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German Pages 1124 [1117] Year 2008
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integraler Querschnitt σ
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10
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2
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0
5
10 15 20 25 30 Streuwinkel Θ /Grad
35 40
45 50
(c)
b1
b 2 b 3 Stoßparameter
c%%P SPXS o2/(.8/$5( u75(848(56&+1,77(\ J$K k17(*5$/( u72M48(56&+1,77( )@5 9$1O'(5Oy$$/6O o2/(.@/(N $8)*(75$*(1 $/6 h81.7,21 '(5 5('8=,(57(1 u72M*(6&+:,1',*.(,7 * 3 +BJT /K 95(/BJ& t0KN (5/$8%(1 (,1( (;3(5,0(17(//( d(67,0081* '(5 g;321(17(1 '(6 $1=,(+(1'(1 81' '(6 $%672O M(1'(1 v(,/6 '(6 9$1O'(5Oy$$/6Or27(17,$/6 xJ5K 3 eSTB5ST 2 eXB5 XP f(5 d(5(,&+6@%(5*$1* %(, * 3 S :,5' %(67,007 '85&+ ',( v,()( & 81' n$*( t0 '(6 r27(17,$/60,1,0806P J%K f,5(5(17,(//( u75(848(56&+1,77( =(,*(1 &+$5$.7(5,67,6&+( NNt(*(1%2*(1DDOu758.785(1 0,7 '(0 '85&+ u72MO (1(5*,( 81' r27(17,$/7,()( %(67,007(1 t(*(1%2*(1675(8:,1.(/ )t 6 T &BgP J&K j$/%./$66,6&+ %(75$&+7(7 (1767(+(1 ',(6( '85&+ k17(5)(5(1= 0(+5(5(5 =80 */(,&+(1 c%/(1.:,1.(/ )@+5(1'(5 u75(875$-(.725,(13)$'( ,1 $1=,(+(1'(1 81' $%672M(1'(1 r27(17,$/%(5(,&+(1P
SSR
S i$6( 81' o2/(.8/$5675$+/(1
SPWPTPU o(6681* ,1(/$67,6&+(5 t27$7,216$15(*81* %(, j(OpTOu7?M(1 g,1 d(,63,(/ )@5 ,1(/$67,6&+( u75(80(6681*(1 =(,*7 c%%P SPXT$ 0,7 (,1(0 h/8*=(,7O 63(.7580 )@5 ',( t27$7,216$15(*81* 921 u7,&.6725Oo2/(.@/(1 '85&+ u7?M( 0,7 j(O /,80 L[ZbP g6 :85'( %(, U[PW@ n$%25675(8:,1.(/ ,1 '(5 =80 pTOv$5*(7675$+/ 6(1.O 5(&+7(1 u75(8(%(1( *(0(66(1N ,1 '(5 ',( +?&+67( ,1(/$67,6&+( c89?681* (55(,&+7 :,5'P f,( u72M(1(5*,( %(75>*7 g 3 TYPU 0(xN 1$+( '(5 :$+56&+(,1/,&+67(1 u72M(1(5*,( . v %(, p250$/7(03(5$785P f(5 u7,&.6725Oo2/(.8/$5675$+/ :85'( ,1 (,1(5 f@6(1675$+/O (;3$16,21 35>3$5,(57 81' ,67 =8 0(+5 $/6 ZW@ ,1 6(,1( t27$7,216*581'=867>1'( *(.@+/7P f$6 +20218./($5( pTOo2/(.@/ 75,77 ,1 =:(, '85&+ ',( SVpOm(5163,167$7,67,. %(',1*7(1 o2',7.$7,21(1 $/6 3$5$Ou7,&.6725 JUU@K 0,7 185 81*(5$'=$+/,*(1 t2O 7$7,216=867>1'(1 81' $/6 257+2Ou7,&.6725 JXY@K 0,7 t27$7,216=867>1'(1 - 3 RN TN VN P P P $8)N ',( $86 r$5,7>76*5@1'(1 '85&+ o2/(.@/67?M( 1,&+7 ,1(,1$1'(5 @%(5*(+(1 .?11(1P k1 '(5 63(.7526.23,6&+(1 p27$7,21 :,5' '(5 r$5,7>76=867$1' 0,7 '(5 *5?O M(5(1 d(6(7=81*6:$+56&+(,1/,&+.(,7 ,00(5 $/6 '(5 NN257+2DDON '(5 0,7 '(5 *(5,1*(5(1 k17(16,7>7 $8)75(7(1'( $/6 '(5 NN3$5$DDO|867$1' %(=(,&+1(7P f(5 g1(5*,($%67$1' '(5 3523257,21$/ =8 - J -1SK $167(,*(1'(1 t27$7,216(1(5*,(O 1,9($86 %(75>*7 V&R2T 3 SPW 0(x )@5 '(1 257+2O%(5*$1* -, S -) 3 R S T 81' 67(,*7 $8) V&S2U 3 TPW 0(x %(,0 S S UOt27$7,216@%(5*$1* %(,0 3$5$Ou7,&.6725 $1P f$6 h/8*=(,763(.7580 ,1 c%%P SPXT$ =(,*7 %(, RPYW 0(x c89?681* '(1 (/$67,6&+(1 u75(8O 3($. 92//67>1',* *(75(117 920 j(/,8098*=(,73($. )@5 ',( R S TOt27$7,216$15(*81* %(, Vg 3 SPW 0(x g1(5*,(9(5/867N *()2/*7 921 =:(, :(,7(5(1 r($.6758.785(1 )@5 ',( S S UOt27$7,216$15(*81* '(6 3$5$OpTOc17(,/6 ,0 u7,&.6725675$+/ 81' (,1(0 6(+5 ./(,1(1 T S VOc15(*81*63($.P f$6 %(, t27$7,2167(03(5$785(1 921 (,1,*(1 m(/9,1 12&+ 0,7 SW@ y$+56&+(,1/,&+.(,7 %(6(7=7( - 3 TOp,9($8 '(6 u7,&.67256 )@+57 $8M(5O '(0 $8&+ =8 '(0 ,0 h/8*=(,763(.7580 /,1.6 920 (/$67,6&+(1 r($. 12&+ 6,&+7%$5(1N ./(,1(5(1 T S ROt27$7,216$%5(*81*63($.P c86 9,(/(1 g,1=(/0(6681*(1 $86*(:(57(O
0
He N2 Θ LAB=39.5
el. 1
11.0 2
0
He N2 E=27.3 meV
2
10
total
3 2
dσ /dΩ (10-20 m2)
12.0
103
2
4
10.0
0
101
2
1
100
3 0
(a)
1.7
1.9 1.8 Flugzeit t /ms
2.0
(b)
0
10
4 20 30 Θcm /Grad
40
50
c%%P SPXT J$K h/8*=(,763(.7580 0,7 $8)*(/?67(1 t27$7,216@%(5*>1*(1 )@5 ',( j(OpTOu75(8O 81* JrgR ST 3 SPW 0(xKP J%K f,5(5(17,(//( t27$7,216$15(*81*648(56&+1,77( )@5 j(OpT %(, '(5 J.,1(7,6&+(1K u72M(1(5*,( g 3 TYPU 0(xP g;3(5,0(17$/:(57( J.-0rKN %(5(&+1(7( y(57( J"N A AN OOOKP
SPW o2/(.8/$5675$+/(1
SSS
7(N ',5(5(17,(//( u75(848(56&+1,77( )@5 ',( t27$7,216$15(*81* %(, pTOj(Ou7?M(1 6,1' ,1 c%%P SPXT% *(=(,*7P y,( '(5 727$/( u75(848(56&+1,77 J'$6 ,67 ',( u800( 921 R S RN S S S 81' $//(1 ,1(/$67,6&+(1 m$1>/(1K 6,1' $8&+ '(5 R S TO 81' '(5 S S UOt2O 7$7,216@%(5*$1* '85&+ 67$5.( s8$17(126=,//$7,21(1 *(35>*7N ',( ,1 *52%(5 p>+(581* '(5 h5$81+2)(5Od(8*81* '(5 j(/,80:(//( $1 (,1(5 m8*(/ 0,7 c7205$',86 (17635(O &+(1P f$6 %(2%$&+7(7( r+>120(1 '(5 r+$6(19(56&+,(%81* =:,6&+(1 '(1 (/$67,6&+(1 81' '(1 R S TO527$7,216,1(/$67,6&+(1 d(8*81*60$;,0$ />667 6,&+ $8) ',( n2.$/,O 6,(581* '(5 t27$7,216@%(5*>1*( $8) (,1(1 6(+5 6&+0$/(1 t$1'%(5(,&+ $0 $%672O M(1'(1 m(51 '(6 j(OpTOy(&+6(/:,5.81*6327(17,$/6 =85@&.)@+5(1P f,( *(5,1*)@*,*( t,&+781*6$6&+67 $/6 u&+:,1*81*6(1(5*,( '(6 jhOr52'8.7(6 )5(,*(O 6(7=7P g,1( o2/(.8/$5675$+/678',( ',(6(5 g/(0(17$55($.7,21 J6P L[[bK %(/(*7 ',(6 )@5 (,1( +,(5 ,1 c%%P SPXU *(=(,*7( r52'8.7*(6&+:,1',*.(,769(57(,/81* %(, (,1(5 hOjTO u72M(1(5*,( 921 g 3 YPYR .lB02/ JW ZR 0(xKP c89?681*67(&+1,6&+ ,67 '$6 g;3(5,O 0(17 6(+5 9,(/ 81*@167,*(5 $/6 '$6 =8925 *(=(,*7( j(/,80675(8(;3(5,0(17N '$ '(5 9(5:(1'(7( h/825$720675$+/ '85&+ 7+(50,6&+( |(56(7=81* 921 h/825 (5=(8*7 :85'( 81' (,1( 6(+5 9,(/ %5(,7(5( o2/(.8/$5675$+/*(6&+:,1',*.(,769(57(,/81* %(6,7=7P |8O '(0 .2117( $86 '(7(.7257(&+1,6&+(1 i5@1'(1 185 ',( h/8*=(,79(57(,/81* '(6 6&+:(O 5(5(1 81' '$+(5 .,1(0$7,6&+ 81*@167,*(5(1 jhOr52'8.702/(.@/6 817(568&+7 :(5O '(1P c%%P SPXU$ ,//8675,(57 ',( m,1(0$7,. '(6 g;3(5,0(17(6 Ji/P JSPTUXKAJSPTU[KK 0,7 '(5 J0,77/(5(1K i(6&+:,1',*.(,7 '(6 hOc720675$+/6 81' '(6 jTOv$5*(7675$+/6N 9h 81' 9j N =86$00(1 0,7 '(1 p(:721Om8*(/1 )@5 ',( g1'*(6&+:,1',*.(,7(1 '(6 jhOr52O A '8.7(6 ,1 '(1 x,%5$7,216=867>1'(1 - 3 RN SN T 81' UP f$6 h/8*=(,763(.7580 '(6 jh %(,0 n$%25:,1.(/ )n 3 SZ@ Jc%%P SPXU%K =(,*7 6(+5 ./$5 $86*(35>*7( r($.6758.785(1 )@5 ',( x,%5$7,216=867>1'( - 3 T 81' - 3 U 81' 9?//,*( c%:(6(1+(,7 921 o2/(.@/(1 ,0 u&+:,1*81*6*581'=867$1' - 3 RP f(5 $/6 -A 3 U 0$5.,(57( %(5*$1* ,67 ',( %(, ',(6(0 n$%25:,1.(/ (%(1)$//6 12&+ 6,&+7%$5( 5@&.:>576 *(675(87( m20321(17( '(5 p(:721Om8*(/ )@5 - 3 UN :,( $86 c%%P SPXU$ (56,&+7/,&+P g,1=(/1( t27$7,216@%(5O *>1*( 6,1' 1,&+7 $8)*(/?67P f,( u75(8(5*(%1,66( 6,1' '$+(5 ,1 (,1(0 m21785(1',$O *5$00 ,1 c%%P SPXU& $/6 n$1'.$57( '(5 jhOy,1.(/9(57(,/81* ,0 u&+:(5381.76576O 675(8:,1.(/1 ,0 u&+:(5381.76*7(1 i(6&+:,1',*O .(,769(57(,/81* $86P f,( 1$&+ '(0 f85&+9,(*(1 (,1(5 n$8)675(&.( $8) 81*()>+5 S &0 5>80/,&+( c86'(+181* $1*(:$&+6(1( v(,/&+(1:2/.( 75,57 $8) (,1(1 *52M9>&+,*(1 m$1$/3/$77(1Ou(.81'>5(/(.7521(19(59,(/)$&+(5 $8)N '(5 (,1 9(567>5.7(6 u,*1$/ '(5 k21(1:2/.(19(57(,/81* (5=(8*7N '$6 @%(5 (,1(1 n(8&+76&+,50 921 (,1(5 eefOm$O
SPW o2/(.8/$5675$+/(1
SSU
Ionisationslaser (-334 nm) Extraktionsplatte CCDKamera
Flugzeitrohr
Fiberoptik
gepulste Düse
CD3I/He
Mikrokanalplatten
Repellerplatte
Phosphorschirm
Skimmer
Photolyse-Laser
c%%P SPXV k21(1$%%,/'81*6$33$5$785 =85 6,08/7$1(1 |867$1'6O 81' y,1.(/9(57(,/81*60(6O 681* 921 t($.7,216352'8.7(1 $86 (,1(0 r+272/5(/(.7521(1%,/':$1'/(53/$77( $8)P 1
2 22-Bande Q-Zweig
1 1 -Bande Q-Zweig
y x
(b)
Streuintensität
(a)
(c)
vcm
0
(d)
0
vcm
c%%P SPXW t>80/,&+( k17(16,7>769(57(,/81*6.21785(1 $0 d,/':$1'/(5$86*$1* J2%(5( t(,+(K 81' =85@&.*(5(&+1(7( i(6&+:,1',*.(,769(57(,/81* '(6 efUOr52'8.702/(.@/6 ,0 u&+:(5O 381.761',*(1 '5(,',0(16,21$/(1 c86:(5781* (5+$/7(1( k17(16,7>7648(5O 6&+1,77 ,1 '(5 J9(57,.$/(1K r2/$5,6$7,2165,&+781* '(6 r+272',662=,$7,216/$6(56 $8)*(O 75$*(1P f,( %(,'(1 3520,1(17(1 r($.6 '(5 efUOi(6&+:,1',*.(,769(57(,/81* (17635(O &+(1 '(5 r+272',662=,$7,21 921 o(7+1*,*.(,7 '(6 k2'Ox(5=:(,*81*69(5+>/71,66(6 921 '(0 x,%5$7,216Ot27$7,216O|867$1' '(6 .203/(0(17>5 (5=(8*7(1 efUOt$',.$/)5$*0(17(6P
SPWPU f,$*1267,. 0,7 o2/(.8/$5675$+/0(7+2'(1 d$6,(5(1' $8) o2/(.8/$5675$+/0(7+2'(1 +$%(1 6,&+ c1:(1'81*(1 (17:,&.(/7N ',( %(1$&+%$57( h256&+81*6*(%,(7( %('(87(1' 925$1%5,1*(1P
SPWPUPS j?&+67$89?6(1'( o2/(.@/63(.7526.23,( '85&+ g,1%(7781* ,1 .$/7( j(/,8075?3)&+(1
Düse
Pick-up
Photonenabsorption + Heliumverdampfung
Massenspektrometer
Laserstrahl
c/6 (,1 d(,63,(/ +,(5)@5 ,67 ,1 c%%P SPXX (,1( j(/,8075?3)&+(1Oo2/(.8/$5675$+/$3O 3$5$785 6.,==,(57N ',( (6 (5/$8%7 (,1=(/1( o2/(.@/( ,1 6(+5 .$/7(6N 9@66,*(6 J683(5O 9@66,*(6K j(/,80 %(, &$P RPUZ m(/9,1 (,1=8%(77(1 81' '$5$1 +2&+ $89?6(1'( 237,6&+( u3(.7526.23,( =8 %(75(,%(1P j(/,8075?3)&+(1 0,7 (,1(5 i5?M( =:,6&+(1 WRRR 81' TRRRR j(/,80$720(1 :(5'(1 $/6 6(+5 (1* .2//,0,(57 $8675(7(1'(5 u75$+/ ,1 (,1(5 $8) SRATR m *(.@+/7(1 W ]0 f@6( %(, TR %$5 j(/,80'58&. (5=(8*7 LSRSN SRTbP f,(
c%%P SPXX j(/,8075?3)&+(1$33$5$785 0,7 r,&.83O|(//( =85 g,1/$*(581* 921 o2/(.@/(1 $86 '(5 i$63+$6( 81' 0$66(163(.7520(75,6&+(0 p$&+:(,6 )@5 '(1 '85&+ r+2721(1$%62537,21 ,1'8=,(57(1 j(/,809(5'$03)81*6352=(66P
SPW o2/(.8/$5675$+/(1 COOH
D
Tryptophan in He-Tröpfchen
α
H C NH2 β
γ
D’ B 34900
34940
ν /cm-1
E
F
in Überschallstrahlen A-Progression
CH2
N H
C’ C 34980
SSW
35020
35060
D E
C
A
F
B 34860
34900
34940
34980
ν /cm-1
c%%P SPXY J$K c866&+1,77 $86 '(0 c%62537,21663(.7580 921 (,1*(/$*(57(1 v55.(5 f233/(5O9(5%5(,7(57 6,1' JNNy(//(1=$+/DDOg1(5*,((,1+(,7\ ZRXW &02S (17635,&+7 S (xKP
=8 817(568&+(1'(1 o2/(.@/( :(5'(1 %(,0 f85&+98* '(5 j(/,8075?3)&+(1 '85&+ (,1( 0,7 02/(.8/$5(0 f$03) '(6 r52%(102/(.@/6 *()@//7( u75(8.$00(5N '(5 r,&.O w3O|(//(N (,1*(/$*(57P f(5 *(5,&+7(7( v5?3)&+(1675$+/ '85&+9,(*7 1$&+ '(0 c8675,77 (,1( n$6(5:(&+6(/:,5.81*65(*,21 81' 75,77 ,1 (,1 o$66(163(.7520(7(5 0,7 g/(.752O 1(1675$+/,21,6$725 (,1N '$6 '(1 k21,6$7,216352=(66 @%(5/(%(1'( j(/,80&/867(5)5$*O 0(17( 81' $8&+ ',( (,1*(6&+/266(1(1 e+52023+2502/(.@/( 6(/(.7,9 1$&+:(,67P y,5' 181 '(5 n$6(5 '85&+*(67,007N 62 *(%(1 (,1*(/$*(57( o2/(.@/( ,+5( $8)*(120O 0(1( r+272(1(5*,( $1 '$6 j(/,8075?3)&+(1 $%N 921 '(0 0(+5(5( +81'(57 c720( J352 r+2721K 9(5'$03)(1N '$ ',( 6(+5 *(5,1*( x(5'$03)81*6:>50( 921 j(/,80 185 YPT m 352 Vj(Oc720 %(75>*7P f,( c%62537,21 (,1(6 r+27216 (56&+(,17 '$1$&+ ,0 e/867(5Oo$66(163(.7580 $/6 u,*1$/>1'(581* ,1 '(5 i5?M(125'181* 921 SR@P f$6 (5*,%7 (,1( 6(+5 (0371'/,&+(N 6(+5 6&+21(1'( 81' 6(+5 .$/7( x$5,$17( '(5 o$7O 5,;Ok62/$7,21663(.7526.23,(P c/6 d(,63,(/ )@5 (,1( 63(.7526.23,6&+( c1:(1'81* :,5' ,1 c%%P SPXY (,1 u3(.7580 921 ,1 j(/,8075?3)&+(1 (,1*(/$*(57(0 v51*,* :(5'(1 x(56&+,(%81*(1 921 :(1,*(1 &02S %,6 =8 2UR &02S 81' XR &02S %(, *5?M(5(1 o2O /(.@/(1 %(2%$&+7(7 LSRSbP j,(5 ,67 ',( t27$7,216%$1'(19(5%5(,7(581* '(5 (/(.7521,O 6&+(1 u3(.75(1 80 *87 (,1( i5?M(125'181* *(*(1@%(5 (,1(0 =80 x(5*/(,&+ *(O
SSX
S i$6( 81' o2/(.8/$5675$+/(1
=(,*7(1 f@6(1675$+/63(.7580 5('8=,(57N 62 '$66 63(.7526.23,6&+( u758.785$1$/8%7N ,0 v52&.(1*$667520 '(O 62/9$7,6,(57 81' 0(+5)$&+ *(/$'(1( r527(,1,21(1 :(5'(1 921 $70263+>5,6&+(1 d(',1*81*(1 ,16 x$.880 =80 o$66(163(.7520(7(5 75$16)(5,(57P J%K k0 g/(.752635$//7 ,1 )(,167( v523)(1P J&K |(5)$// *(/$'(1(5 v523)(1 '85&+ |(5635(1*81* 2'(5 '85&+ 9(567>5.7( x(5'$03)81* %(, %(5:,(*(1 '(5 e28/20%Om5>)7( @%(5 ',( q%(59>&+(163$1181*P
SPW o2/(.8/$5675$+/(1
SSY
SPWPUPT g/(.752635$1',* 81' (6 %/(,%7 '$6 8162/9$7,6,(57( o2/(.@/ 0,7 (,1(0 2'(5 0(+5(5(1 $1*(/$*(57(1 r52721(1 =85@&.P h(/' 81' i$667520 %(:,5.(1 '(1 v5$163257 =85 v5$16)(5.$3,//$5(1 81' ,1 '$6 x$O .880680/,&+(1 c86'(+181* '(5 9@66,*(1 y$66(52%(59>&+( $8) c%0(6681*(1 817(5+$/% '(5 )5(,(1 y(*/>1*( '(6 -(:(,/,*(1 h/@66,*.(,76'$03)(6P g,1( 35$.7,.$%/( t($/,6,(581* (,1(5 x$.8802%(59>&+( '(6 9@66,*(1 y$66(56 (5+>/7 0$1 0,7 (,1(0 ,16 x$.880 675?0(1'(1 =&+( =80 }48,9$/(17 (,1(5 )5(,(1 o2/(.8/$5675$+/48(//(N $86 '(5 y$66(502/(.@/( 2+1( 1$&+)2/*(1'( u7?M( ,16 x$.880 $8675(7(1P f$*(*(1 75(7(1 %(, *5?M(5(1 c%0(6681O *(1 '(5 y$66(59>&+( %(, 819(5>1'(57(0 f$03)'58&. =81(+0(1' u7?M( ,1 '(5 i$6O 3+$6( 81' (,1( 1$&+)2/*(1'( +&+( $86*(+(1'( f$03)675$+/ :,5' =8 (,1(0 %(56&+$//02/(.8/$5675$+/ 0,7 $167(,*(1'(0 i(6&+:,1',*.(,769(5+>/71,6 uP i/(,&+=(,7,* :,5' '$%(, ',( )@5 o2/(.8/$5675$+/%(2%$&+781*(1 '(5 y$66(52%(59>&+( %(1?7,*7( 81*(67?57( u75$+/$86%5(,781* =81(+0(1' %(+,1'(57P f,(6(5 |86$00(1O +$1* :,5' ,1 (,1(0N (%(1)$//6 ,1 c%%P SPYR 6.,=,(57(1 o2/(.8/$5675$+/Oh/8*=(,7(;O 3(5,0(17 $0 6(1.5(&+7 =85 h/@66,*.(,76675$+/$&+6( $8675(7(1'(1 y$66(5'$03) %(O 67>7,*7P f85&+ (,1( ,1 W 00 c%67$1' 6(,7:>576 920 h/@66,*.(,7675$+/ $1*(%5$&+7( u.,00(5?5181* 75,77 921 (,1(0 925*(*(%(1(1 6&+0$/(1 c%6&+1,77 '(6 h/@66,*.(,76O
Wasserdüse p=80 bar
glatter p=10-6 mbar zylindrischer Strahlabschnitt >3 mm
6.3 µm
Kühlfalle
Dampf Skimmer Dampfstrahl zum MolekulargeschwindigkeitsFlugzzeitspektrometer
(a)
Zählrate pro TOF-Kanal/Max
1.0
(b)
D =50 µm
D =10 µm
H2O
0.5
0
0
1.0 Flugzeit t /ms
2.0
3.0
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TVX
T p,('(57(03(5$7853/$60(1 Aston- KathodenFaraday-Dunkelraum Dunkelraum
Schichtung
Anoden-Dunkelraum
positive Säule KathodenGlimmlicht
(a)
negatives Glimmlicht
Anoden-Glimmlicht
ΦA Φ
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TVY
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0.27 cm 0.42 cm
x =0 cm Kathode
0.57 cm 0.72 cm 0.87 cm 1.02 cm 1.17 cm 1.32 cm
x
0 50 100 150 /eV normale Glimmentladung
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TVZ
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A
A
Schnitt A-A Beobachtung
(a)
Kühlwasser und elektrischer Anschluss
Gaszufuhr
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Schmelze
Abflussöffnung für Schmelze Austrittsdüse (b)
Elektrode
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21000
15000
Argon R E = 0.15 cm
200 A
Stickstoff R E = 1 cm
100 A 30 A
19000
10000
150 A
20 A 15 A
17000
T/K 100 A
15000 13000 11000 (a)
19 A
T/K 5000
50 A
0
0.2
0.4 ρ
0.6
0.8
0 (b)
0
0.2
0.4
ρ
0.6
0.8
1.0
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20
Argon 200 A
10
200 A
100 A
5 3 2
50 A
1 0.5 (a)
Helium
400 A
5 3 2 ne /1022 m-3
ne /1022 m-3
10
100 A
400 A
300 A 200 A
1 100 A
0.5 0.3 0.2 0.1
8
10
12 14 Te /103 K
16
18
20
12
22 (b)
14
16
18 20 Te /103 K
22
24
26
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uJvK 3 g + JvK 'v P v ~
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T p,('(57(03(5$7853/$60(1 120 Argon
σ /102Ω -1m-1
100 80 60 40 20
11
13
15 T/103 K
17
19
21
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Argon
2.8 2.4
W (mK)
1.6
λ
2.0
1.2 0.8 0.4 0
0
2
4
6
8 10 12 14 Temperatur T/103 K
16
18
20
22
24
6
8 10 12 14 Temperatur T/103 K
16
18
20
22
24
(a) 6 Stickstoff
5
λ
W (mK)
4 3 2 1 0 (b)
0
2
4
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T p,('(57(03(5$7853/$60(1
Mantelgasstrom Zentralgasstrom Trägergasstrom
(a)
Spule
15 slm Ar Sonde Trägergas: 5 slm Ar 150 (b)
130
110
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70
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150
130
110
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30 25 20 15 10 5 0
x /mm
Mantelgas: 120 slm Ar Zentralgas:
T /K
Spule
0
30
30 25 120 slm Ar 20 Zentralgas: 15 15 slm Ar 10 5 Sonde 0 Trägergas: 5 slm Ar Mantelgas:
48
30
x /mm
Quarzrohr
10000 8000 6000 4000 2000 0
0
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〈 E 〈 1000 K
0.25
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NPE -1.5
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Nullpunktsenergie (NPE) 1.0
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kR /cm3 mol-1 s-1
109
O+H2
6
OH+H
10
103
O+H2O 0
c%%P UPZ
OH+HO2
2 1 1000 1 T K
2OH
3
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81'
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USZ
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300K
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kR /k ∞ 0.10
1350K
0.05 -1
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0
1
3 2 lg(p/mbar)
2000K
4
5
6
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2
OH + H2
H2O + H
H
+ H2O
OH
+ H2
H
+ O2
OH
+ O
OH + O
H
+ O2
OH + OH
H2O + O
O
OH
+ H2O
HO2 + M
CO + OH
CO2 + H
H
+ CO2
CO
O
+ CH3
CH2O + H
OH + O
+ OH
H+CH3(+M)
CH4 (+M)
H
H2
+ CO
CHO + M
CO + H + M
C2H5 (+M)
C2H4+H(+M)
O
CH2 + CO
+ C2H2
H + O2
+ OH
H + O2 + M
+ CHO
vL vL(kR/5)
3
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UPUPS n,1($5( /$6(563(.7526.23,6&+( x(5)$+5(1 g,1( 63(.7526.23,6&+( v(&+1,. :,5' /,1($5 *(1$117N :(11 (,1( /,1($5( d(=,(+81* =:,6&+(1 '(5 |$+/ '(5 u,*1$/3+2721(1 81' '(5 =85 o(6681* (,1*(6(7=7(1 n$6(53+2O 721(1 6n (;,67,(57 Jc%%P UPSSKP
Laserabsorptionsspektroskopie (LAS)
N2 ωL
N1 Rayleigh-Streuung (RS)
ωL
ω RS
laserinduzierte Fluoreszenz (LIF)
ωL l
P W ω LIF b b21 A21 Q21 N2 12 N1
Filter
spontane Raman-Streuung (SRS)
ωL
ωS Filter
c%%P UPSS
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1
0
f$%(, ,67 . ',( d2/7=0$11Om2167$17( 81' & (,1( m$/,%5,(5.2167$17(N ',( ',( (9(178(// 817(56&+,('/,&+(1 c15(*81*6O 81' f(7(.7,216%(',1*81*(1 %(, %(,'(1 c15(*81*6O :(//(1/>1*(1 %(5@&.6,&+7,*7 81' '85&+ x(5*/(,&+ 0,7 (,1(0 v(03(5$78567$1'$5' J=P dP (,1(5 m$/,%5,(59$00(K *(:211(1 :,5'P f,( o(6681* ,67 81$%+>1*,* 921 '(5 /2.$/(1 m21=(175$7,21 '(5 c1$///(1 '(5 6,08/7$1( g,16$7= 921 0(+5 $/6 =:(, y(//(1/>1*(1 8135$.7,.$%(/P g,1( |:(,On,1,(1Oo(6681* ,67 '$+(5 ,1 9,(/(1 h>//(1 (,1 m203520,66 =85 v(03(5$7850(6681* ,1 785%8/(17(1 81' 620,7 =(,7/,&+ 9$5,$%/(1 o(662%-(.7(1P |85 nkhOv(03(5$7850(6681* :,5' +>87* qj (,1*(6(7=7P j,(5%(, ,67 0$1 -('2&+ $8) t(*,21(1 %(6&+5>1.7N ,1 '(1(1 qj 0,7 $865(,&+(1'(5 m21=(175$7,21 ,1 '(5 2300
15 10 4 5 -10 -5 0 10 Abstand zur Brennerachse/mm
(a) 2500
Temperatur/K
2000
(b)
Temperatur/K
Höhe über Brenner/mm
20
Höhe über Brenner 9 mm
14 mm
250
19 mm
1500 1000 500 -10 -5
0
5
10
-10 -5 0 5 10 -10 -5 Abstand zur Brennerachse/mm
0
5
10
c%%P UPSU v(03(5$7850(6681* 0,7 nkh $1 u7,&.2;,' ,1 (,1(5 /$0,1$5(1 d816(1%5(11(59$0O 0(P t(&+76\ x(5*/(,&+ 921 $86 '(1 =:(,',0(16,21$/(1 d,/'(51 (;75$+,(57(1 r527/(1 0,7 ectuO r81.70(6681*(1 J6P c%6&+1P UPUPTPSK LUSN UTbP
UUT
U x(5%5(1181*
h/$00( $8)75,77P f85&+ |8*$%( 921 pq 81' d(2%$&+781* '(5 pqOnkh .$11 0$1 ',(6( g,16&+5>1.81* 80*(+(1P k1 c%%P UPSU ,67 (,1( =:(,',0(16,21$/( v(03(5$785O 0(6681* 0,7 j,/)( 921 pqOnkh ,0 x(5*/(,&+ 0,7 ectuOr81.70(6681*(1 J9*/P c%O 6&+1P UPUPTPSK '$5*(67(//7P
UPUPSPU t$1'(5/,&+( f,32/020(17 ],1' 67(//7 :,('(580 (,1( s8(//( )@5 (/(.7520$*O 1(7,6&+( u75$+/81* '(5 h5(48(1= -R '$5P o$1 .$11 '(1 r52=(66 $/6 c%675$+/81* (,1(6 j(57=I6&+(1 f,32/6 $85$66(1N '(5 '85&+ '$6 26=,//,(5(1'( (/(.75,6&+( h(/' '(5 (,1/$8)(1'(1 n,&+7:(//( =8 u&+:,1*81*(1 $1*(5(*7 :,5'P f$6 (0,77,(57( n,&+7 ,67 '$+(5 32/$5,6,(57 81' :(,67 (,1( 67$5. $1,627523( y,1.(/9(57(,/81* $8)P k0 h$// '(5 (/$67,6&+(1 u75(881* +$7 '$6 (,1)$//(1'( 81' (0,77,(57( r+2721 ',(6(/%( y(//(1/>1*(P f,(6(5 r52=(66 :,5' $/6 t$1*(5(1 JNNu72.(6DDK 2'(5 .@5=(5(1 JNNc17,Ou72.(6DDK y(//(1/>1*(1 9(56&+2%(1P f,( x(56&+,(%81* ,67 63(=,(6663(=,76&+ 81' ,+5 d(75$* ,67
UPU n$6(563(.7526.23,( 921 x(5%5(1181*6352=(66(1
UUU
'(5 (,1(6 2'(5 0(+5(5(5 u&+:,1*81*6O 2'(5 t27$7,21648$17(1P f,( k17(16,7>7 '(5 t$0$1Ou75(881* />667 6,&+ $1$/2* '(5 '(5 t$1*( '(6 u75(8/,&+76 =8P f$ ',( u75(8%(,75>*( '(5 9(56&+,('(1(1 u3(=,(6 %(, 817(56&+,('/,&+(1 h5(48(1=(1 $8)75(7(1N .$11 %(, 63(.75$/(5 v5(1181* '(6 (0,77,(57(1 n,&+76 810,77(/%$5 J0,7 (,1(0 (,1=(/1(1 n$6(538/6K ',( |86$00(1O 6(7=81* '(5 /2.$/(1 i$60,6&+81* %(67,007 :(5'(1P f,(6 ,67 %(621'(56 :,&+7,* )@5 9(5%5(1181*65(/(9$17( v(,/&+(1 :,( pT 81' jTN ',( 0,7+,/)( 921 c%62537,216O 81' h/825(6=(1=9(5)$+5(1 185 %(, 6(+5 .85=(1 y(//(1/>1*(1 (5)$667 :(5'(1 .?11(1N ',( 817(5 '(1 %(, x(5%5(1181*6352=(66(1 +(556&+(1'(1 d(',1*81*(1 -('2&+ 1,&+7 0(+5 75$160,77,(57 :(5'(1P q%:2+/ '(5 r52=(66 6(+5 /,&+76&+:$&+ ,67 J'$6 x(5+>/71,6 kt$0$1Bk Rn$6(5 %(75>*7 (7:$ SR2SVN t$7(1 921 u72.(6O 81' c17,O u72.(6Og0,66,21 921 pTKP
UPUPSPW n$6(5,1'8=,(57( k1.$1'(6=(1= JnkkK t8M 63,(/7 ,1 =$+/5(,&+(1 x(5%5(1181*6352=(66(1 (,1( *52M( t2//(P g5 ,67 )@5 '$6 71',* 9(5%5$117(5K t8M *,/7 -(O '2&+ $/6 (,1 :(6(17/,&+(5N 921 x(5%5(1181*6352=(66(1 *(1(5,(57(5 u&+$'6725P f,( NNt8M.21=(175$7,21DD :,5' ,1 '(5 t(*(/ '85&+ '(1 t8M92/80(1%58&+ )x %(6&+5,(%(1N '(5 '$6 x(5+>/71,6 '(6 921 t8M (,1*(1200(1(1 x2/80(16 =80 i(6$0792/80(1 '(5 r52%( '$567(//7P k1 u,78$7,21(1N ,1 '(1(1 6,&+ ',( t8M9(57(,/81* =(,7/,&+ 1,&+7 9(5>1'(57 81' (,1( %(.$117( u1*,*.(,7(1 920 r$57,.(/'85&+0(66(5 .$11 '85&+ '$6 x(5O +>/71,6 921 u75(8/,&+7,17(16,7>7 81' g;7,1.7,21 $8) 0,77/(5( /2.$/( f85&+0(66(5 *(O 6&+/266(1 :(5'(1P u,( :(5'(1 $8)*581' '(5 c57 '(5 o,77(/81* ,1 i/P JUPW[K $/6 fXUO f85&+0(66(5 %(=(,&+1(7P f,( r$57,.(/*5?M(19(57(,/81* :,5' '$%(, '85&+ ',( '85&+O 0(66(5$%+>1*,*( j>87*.(,769(57(,/81* rJ5K %(6&+5,(%(1P fXU 3 T
0 1
9 9 u75(881* %5N& I K6 0,7 %5N& 3 g rJ5K5N'5 81' %5K& 3 g rJ5K5K'5JUPW[K g;7,1.7,21 %5K& R R
U x(5%5(1181* spektrale Strahlungsdichte/w.E.
UUV
18 16 14 12 10 8 6 4 2 0 200
T=4000 K
T=2000 K(×10) 600 1000 Wellenlänge/nm
1400
1800
c%%P UPSV u3(.75$/( u75$+/81*6',&+7( (,1(6 6&+:$5=(1 u75$+/(56 )@5 v 3 TRRR m J9(567>5.7 0,7 h$.725 SRK 81' v 3 VRRR mP
f$ ',( g;7,1.7,2160(6681* 185 ,17(*5$/ @%(5 ',( '85&+/$8)(1( y(*675(&.( '(6 n$6(56 %(2%$&+7(7 :(5'(1 .$11N ,67 (,1( 2576$8)*(/?67( o(6681* '(6 t8M92/80(1%58&+6 2'(5 '(5 0,77/(5(1 r$57,.(/*5?M( ,1 785%8/(17(1 h/$00(1 J=P dP ,0 x(5%5(1181*6O 02725K 1,&+7 0?*/,&+P c8)*581' '(5 i5?M( '(5 r$57,.(/ .?11(1 )@5 '(1 /$6(563(.O 7526.23,6&+(1 p$&+:(,6 -('2&+ '(5(1 h(67.?53(5(,*(16&+$)7(1 *(187=7 :(5'(1P k1 '(5 h/$00( 6,1' ',( r$57,.(/ ,1 '(5 t(*(/ $8) v(03(5$785(1 921 SWRR A TRRR m $8)*(+(,=7P f,( (0,77,(57( u75$+/81* +$7 (,1 9$&+(6 o$;,080 ,0 1$+O,1)5$527(1 u3(.75$/%(5(,&+ J80 SXXR 10KP y,5' '(5 t8M '$*(*(1 0,7 (,1(0 n$6(5675$+/ .85=O )5,67,* %,6 =85 x(5'$03)81*6*5(1=( $8)*(+(,=7 J80 VRRR mKN 9(56&+,(%7 6,&+ 1$&+ '(0 r/$1&.Oi(6(7= J6P d'P UN m$3P WPTK '$6 g0,66,2160$;,080 1,&+7 185 '(87/,&+ =8 .@5=(5(1 y(//(1/>1*(1 J=8 &$P YRR 10KN $8)*581' '(6 u7()$1Od2/7=0$11Oi(6(7=(6 1,007 $8&+ ',( *(6$07( c%675$+/81* t 6 v V 67$5. =8 6P Jc%%P UPSVKP y>+5(1' '(5 n$6(5%(675$+/81* 1,007 ',( g0,66,21 %(, y(//(1/>1*(1 80 VRR A WRR 10 80 0(+5(5( i5?M(125'181*(1 =8N 62 '$66 '$6 nkkOu,*1$/ '(5 t8M0(1*( A 81$%+>1*,* 921 '(5 /2.$/(1 1$7@5/,&+(1 h/$00(1(0,66,21 A =8*(25'1(7 :(5'(1 .$11P f,( =(,7$%+>1*,*( v(03(5$7859(5>1'(581* 81' ',( '$5$86 5(68/7,(5(1'( nkkO u,*1$/,17(16,7>7 .?11(1 $8) '(5 d$6,6 (,1(5 g1(5*,(%,/$1=,(581* 02'(//,(57 :(5'(1N ,1 '(5 *(0>M c%%P UPSW '(5 g1(5*,((,175$* '85&+ n,&+7$%62537,21 '(1 817(56&+,('O /,&+(1 x(5/8673)$'(1 *(*(1@%(5*(67(//7 :,5'P c86 '(5 d,/$1=,(581* '(5 ,1 c%%P UPSW *(1$117(1 r52=(66( *(+7 +(5925N '$66 81O 7(5+$/% 921 UURR m ',( y>50(/(,781* '(5 '20,1$17( r52=(66 %(, '(5 g1(5*,($%*$%( ,67N 2%(5+$/% 921 UYRR m @%(5:,(*7 ',( x(5'$03)81*P g567 ,0 h$//( 921 v(03(5$O 785(1 2%(5+$/% SR RRR m :@5'( ',( u75$+/81* '(1 j$837$17(,/ $860$&+(1P f,( d,O /$1=,(581* )@+57 (%(1)$//6 =8 (,1(5 .203/,=,(57(1 c%+>1*,*.(,7 '(6 =(,7$%+>1*,*(1 nkkOu,*1$/6 921 '(5 n$6(5(1(5*,(',&+7( 81' '(1 w0*(%81*6%(',1*81*(1P c8)*581' '(5 =81(+0(1'(1 c8)+(,=81* '(5 r$57,.(/ 67(,*7 %(, *(5,1*(1 n$6(5(1(5*,(',&+7(1 ',( u,*1$/,17(16,7>7 =81>&+67 0,7 kn$6(5 $1P g55(,&+(1 ',( $8)*(+(,=7(1 r$57,.(/ $//(5O ',1*6 ',( x(5'$03)81*67(03(5$785N )@+57 (,1( :(,7(5( u7(,*(581* '(5 n$6(5(1(5*,( 1,&+7 =85 :(,7(5(1 v(03(5$785O 81' 620,7 nkkOk17(16,7>7667(,*(581*P g6 :,5' (,1( NNr/$7($8=21(DD '85&+/$8)(1P y(,7(5(6 c8)+(,=(1 6(1.7 '$*(*(1 ',( u,*1$/,17(16,7>7N :(,/ %(5(,76 :>+5(1' '(5 n$6(538/6'$8(5 (,1 1(11(16:(57(5 c17(,/ '(5 r$57,.(/0$66(
UPU n$6(563(.7526.23,( 921 x(5%5(1181*6352=(66(1
UUW
- 4 πr 3ρsCp.s dT 3 dt Anstieg der inneren Energie U Laser Qabs(r ).πr 2I
-
Rußpartikel
Ka (T-T0)(4πr 2) r
(1+GKn)
∆Hν dM Wν dt Verdampfung -
4
- σSBε λ (T 4-T 0)(4πr 2) Strahlung
Wärmeabführung
c%%P UPSW g1(5*,(%,/$1= %(, '(5 n$6(5$8)+(,=81* 921 t8MP s$%6\ y,5.81*648(56&+1,77 )@5 ',( c%62537,21] k\ k17(16,7>7 '(5 n$6(5675$+/81* LyB0Tb] 5\ r$57,.(/5$',86] m$\ y>50(/(,7)>O +,*.(,7 LyBJ0 mKb] v\ r$57,.(/7(03(5$785 Lmb] vR\ h/$00(17(03(5$785 Lmb] i\ *(20(75,($%O +>1*,*(5 y>50(/(,7)>+,*.(,76)$.725] m1\ m18'6(1O|$+/] (j9\ x(5'$03)81*6(17+$/3,( 921 m2+/(16725 LlB02/b] y9\ o2/(.8/$5*(:,&+7 921 '$035?50,*(0 m2+/(16725 L.*B02/b] o\ r$57,.(/0$66( L.*b] 1ud\ u7()$1Od2/7=0$11Om2167$17(] &+\ g0,66,9,7>7 921 m2+/(16725] 06\ f,&+7( 921 m2+/(16725 L.*B0Ub] e3N6\ 63(=,76&+( y>50(.$3$=,7>7 921 m2+/(16725 LlBJ.* mKbP f,( g,1+(,7(1 ,1 m/$00(51 :(5'(1 @%/,&+(5:(,6( )@5 ',( $1*(*(%(1(1 i5?M(1 9(5:(1'(7P
9(5'$03)7P h@5 9,(/( 7(&+1,6&+( c1:(1'81*(1 :(5'(1 '$+(5 n$6(5(1(5*,(1 (,1*(O 6(7=7N ',( '$6 g55(,&+(1 '(5 r/$7($8=21( (5/$8%(1P f,( o(6681* ,67 '$0,7 :(,7*(+(1' 81$%+>1*,* 921 '(5 /2.$/(1 n$6(5,17(16,7>7 81' '(5 h(+/(5 '85&+ c%6&+:>&+81* '(6 n$6(5675$+/6 '85&+ g;7,1.7,21 ,67 0,1,0,(57P h@5 ./(,1( r$57,.(/ (5*,%7 6,&+ ',( ,1 i/P JUPXRK %(6&+5,(%(1( c%+>1*,*.(,7 '(5 nkkOk17(16,7>7 921 '(5 t8M7(,/&+(1*5?M(P f(5 g;321(17 ,67 1$+( UP f$+(5 .$11 ',( nkkOk17(16,7>7 $/6 o$M )@5 '(1 t8M92/80(1%58&+ )x ,17(535(7,(57 :(5'(1P 9
knkk 6 g p r J5K 5 ; '5 . )x 0,7 ; 3 U 1 R
RPSWV P +'(7
JUPXRK
f$ ',( nkkOk17(16,7>7 921 =$+/5(,&+(1 (;3(5,0(17(//(1 r$5$0(7(51 $%+>1*7N ,67 =85 s8$17,7=,(581* '(5 o(6681* (,1( m$/,%5$7,21 (5)25'(5/,&+P j,(5=8 :(5'(1 m$/,%5$O 7,2169$00(1 (,1*(6(7=7N ,1 '(1(1 '(5 t8M92/80(1%58&+ 925$% '85&+ g;7,1.7,216O 0(6681*(1 (50,77(/7 :85'( 81' ,1 '(1(1 ',( nkkOk17(16,7>7 =85 g50,77/81* '(5 m$O /,%5$7,216.2167$17( &&$/,% 817(5 0?*/,&+67 ,'(17,6&+(1 d(',1*81*(1 :,( ,1 '(5 1$&+O )2/*(1'(1 o(6681* J%=*/P c15(*81*6O 81' f(7(.7,216:(//(1/>1*(1N n$6(5(1(5*,(O ',&+7(N =(,7/,&+(5 u,*1$/,17(*5$7,21 81' d(2%$&+781*6*(20(75,(K %(67,007 :,5'P w1O 7(5 ',(6(1 t$1'%(',1*81*(1 .$11 (,1 (,1)$&+(5 |86$00(1+$1* )@5 ',( nkkOk17(1O 6,7>7 knkk 3 &&$/,% )9
JUPXSK
$1*(1200(1 :(5'(1P f(5 nkkOr52=(66 ,67 9(5*/(,&+6:(,6( /,&+767$5.P |:(,',0(16,2O 1$/ $8)*(/?67(N %,/'*(%(1'( o(6681*(1 '(5 t8M92/80(1%5@&+( =P dP ,1 h/$00(1 6,1' '$+(5 0?*/,&+P f85&+ m20%,1$7,21 0,7 (%(1)$//6 $%%,/'(1'(1 u75(8/,&+70(6O
UUX
U x(5%5(1181*
681*(1 .$11 $1$/2* '(5 2%(1 *(1$117(1 r$57,.(/*5?M(10(6681*(1 0,7 g;7,1.7,216O 81' u75(8/,&+70(6681* (%(1)$//6 @%(5 nkk 81' u75(8/,&+7 (,1 0,77/(5(5 fXUOf85&+O 0(66(5 (50,77(/7 :(5'(1P p(8( o(6681*(1 =85 d(67,0081* 921 r$57,.(/*5?M(1 187O =(1 '$6 |(,79(5+$/7(1 '(5 nkkOk17(16,7>7P u,( %(58+(1 '$5$8)N '$66 *5?M(5( r$57,.(/ 1$&+ '(0 c8)+(,=(1 '85&+ n$6(5675$+/81* /$1*6$0(5 $%.@+/(1 $/6 ./(,1(P
UPUPT p,&+7/,1($5( /$6(563(.7526.23,6&+( x(5)$+5(1 d(, '(1 0,7 n$6(51 (55(,&+%$5(1 +2+(1 n,&+7,17(16,7>7(1 .$11 6,&+ (,1 1,&+7/,1($5(5 |86$00(1+$1* =:,6&+(1 d(675$+/81*6,17(16,7>7 81' o(66*5?M( (,167(//(1N '(5 (5670$/,* )@5 ',( |:(,3+2721(1$%62537,21 925+(5*(6$*7 :85'( LUUbP y,( ,1 c%%P UPSX 6&+(0$7,6&+ '$5*(67(//7N .(+57 '$6 817(568&+7( o2/(.@/(16(0%/( 1$&+ (,1(5 */(,&+O =(,7,*(1 y(&+6(/:,5.81* 0,7 0(+5(5(1 r+2721(1 '85&+ c866(1'81* (,1(6 u,*1$/O 3+27216 :,('(5 ,1 '(1 c86*$1*6=867$1' =85@&.P f$%(, :,5' @%(5 ',( +?+(5(1 q5'O 181*(1 '(6 63(=,76&+(1 u86=(37,%,/,7>767(16256 J6P d'P UN m$3P [PTK (,1( 1,&+7/,1($5( r2/$5,6$7,21 '(6 o(',806 (5=(8*7N ',( =85 g0,66,21 '(6 u,*1$/3+27216 )@+57P g,1 .2+>5(17(6 u,*1$/ A 81' '$0,7 (,1( 80 i5?M(125'181*(1 (5+?+7( u,*1$/,17(16,7>7 A (1767(+7 -('2&+ 185 '$11N :(11 (,1( r+$6(1$13$6681* $//(5 u75$+/(1 J'(5 (,1)$/O /(1'(1 $/6 $8&+ '(5 ,0 o(',80 (5=(8*7(1K (55(,&+7 :,5'N 62 '$66 (,1( .216758.7,9( c'',7,21 '(5 0,.526.23,6&+(1 u75(8%(,75>*( (,175,77 81' ',( k038/6(5+$/781* *(O :>+5/(,67(7 :,5'\ X6,* 3 } X- N -
:2%(, # X- # 3
6, T@ 3 +&
JUPXTK
'(5 y(//(19(.725 '(6 (17635(&+(1'(1 r803/$6(5675$+/6 ,67P f85&+ ',( h2.866,(581* '(5 r803675$+/(1 .$11 (,1( +2+( q576$89?681* ,0 =0Od(5(,&+ 6(1.5(&+7 =85 r803O 675$+/$86%5(,781*65,&+781* 2+1( :(6(17/,&+( x(5/867( $1 u,*1$/,17(16,7>7 (55(,&+7 :(5'(1P
kohärente Anti-Stokes-Raman-Streuung (CARS) ω CARS =2ω1 _ ω 2
entartete 4-Wellen-Mischung (DFWM) ω DFWM =2 ω 1 _ ω 1
ω1 ω 2 ω1
ω1
ω DFWM
(a)
(b)
Polarisationsspektroskopie (PS) ω PS =2ω 1 _ ω 1
resonante Mehrphotonen-Ionisation (REMPI) n ω 1 + mω 2 > ω ion + eω2 NK ω1 N1 (d)
ω1 (c)
c%%P UPSX
ω CARS
ω PS
u&+(0$7,6&+( f$567(//81* (,1,*(5 1,&+7/,1($5(5 /$6(563(.7526.23,6&+(5 x(5)$+5(1P
UPU n$6(563(.7526.23,( 921 x(5%5(1181*6352=(66(1
UUY
UPUPTPS m2+>5(17( c17,Ou72.(6Ot$0$1Ou75(881* m2+>5(17( c17,Ou72.(6Ot$0$1Ou75(881* JectuK /,()(57 ,0 x(5*/(,&+ =85 63217$1(1 t$0$1Ou75(881* 80 %,6 =8 )@1) i5?M(125'181*(1 ,17(16,9(5( u,*1$/(P c8)*581' '(6 .2+>5(17(1 u,*1$/675$+/6 %(1?7,*7 ectu $8M(5'(0 :(6(17/,&+ ./(,1(5( 237,6&+( |8*$1*6?5181*(1 81' ,67 :(,7*(+(1' 81(0371'/,&+ *(*(1@%(5 h/825(6=(1=675$+O /81* 81' g,*(1/80,1(6=(1=(1 '(6 817(568&+7(1 o(662%-(.76P ectuOu75(8352=(66( (1767(+(1 ,1 (,1(5 x,(5:(//(1:(&+6(/:,5.81*N :2%(, '5(, ,17(16,9( n$6(5675$+/(1 ,0 6,&+7%$5(1 u3(.75$/%(5(,&+ 0,7 '(1 h5(48(1=(1 6S JSP 81' TP r803675$+/K 81' 6T Ju72.(6Ou75$+/K @%(5/$*(57 :(5'(1N '(5(1 h5(48(1=.20%,1$7,21 6ectu 3 6U 3 T6S 26T '(5 y(//(1/>1*( (,1(6 t$0$1O(5/$8%7(1 c17,Ou72.(6O%(5*$1*6 (17O 635,&+7P f$+(5 ,67 '(5 u,*1$/675$+/ 63(.75$/ 81' $8)*581' '(5 127:(1',*(1 r+$6(1O $13$6681* $8&+ 5>80/,&+ 921 '(1 (5=(8*(1'(1 u75$+/(1 *(75(117 81' :,5' ,1 (,1(0 o212&+520$725 $1$/1*7 ',( ectuOu,*1$/,17(16,7>7 *(0>M i/P JUPXUK 920 r52'8.7 '(5 (,1*(675$+/7(1 n$6(5,17(16,7>7(1 k, J(6 :(5'(1 '$+(5 0(,67 *(38/67( 81' )2.866,(57( n$6(5675$+/(1 +2+(5 k17(16,7>7 0,7 (,1(5 r8/6'$8(5 921 (7:$ SR2Z 6 9(5:(1'(7KN '(0 s8$'5$7 '(5 y(&+6(/:,5.81*6/>1*( /N '(5 v(,/&+(1',&+7( '(5 %(2%$&+7(7(1 u3(=,(6 p 81' '(5 5(/$7,9(1 d(6(7=81*6',5(5(1= (- '(5 %(,'(1 '85&+ '(1 t$0$1Or52=(66 *(.233(/7(1 |867>1'( $%P g6 6,1' 1, ',( d5(&+81*6,1',=(6 %(, '(1 %(7(,/,*7(1 y(//(1/>1*(1N C- '(5 x(5%5(,7(581*6.2(5,=,(17 J3523257,21$/ =85 n,O 1,(1%5(,7( '(5 63217$1(1 t$0$1Ou75(881*KN (6- ',( 63(.75$/( c%:(,&+81* 921 '(5 t(621$1=)5(48(1= 81' '1B'\ '(5 ',5(5(17,(//( t$0$1Ou75(848(56&+1,77P x21 =(17O 5$/(5 d('(8781* ,1 i/P JUPXUK ,67 ',( u86=(37,%,/,7>7 UP q5'181* 4JUKN ',( 921 '(5 v(0O 3(5$785 81' '(5 |86$00(16(7=81* '(6 817(568&+7(1 o(',806 $%+>1*7P y(6(17/,&+( o(5.0$/( 921 4JUK .?11(1 %(5(,76 ,0 ./$66,6&+(1 d,/' '(6 *('>03)7(1 q6=,//$7256 817(5 g,19866 (,1(5 75(,%(1'(1 (/(.7520$*1(7,6&+(1 m5$)7 $%*(/(,7(7 :(5'(1P f,( =81>&+67 UV 921(,1$1'(5 81$%+>1*,*(1 m20321(17(1 '(6 v(16256 4JUK :(5'(1 '85&+ ',( u1O *,*(1 u&+5?',1*(5Oi/(,&+81* )@5 (,1 g16(0%/( 921 p o2/(.@/(1 LUVbP f,( c%%P UPSY =(,*7 '(1 237,6&+(1 c8)%$8 (,1(6 71*(1 67$5. 921 '(5 v(03(5$785 Jc%%P UPSYK 81' '(0 f58&. $%P
U x(5%5(1181*
Nd:YAG-Laser
Verdopplerkristall
ω1 Breitbandfarbstofflaser
T =2030 K
ω2
CARS-Intensität/w.E.
UUZ
Amplitude
( χ’’≤ χ’+ χ nr )
χ (3)
(4)
2
(2) (3) (1)
δ =ω -ω 0
ω0
Monochromator/ Spektrometer
(a)
T =1000 K
T =300 K
P/CCD
ω CARS
(b)
2290 2300 2310 2320 2330 2340 Raman-Verschiebung/cm-1
c%%P UPSY J$K u&+(0$7,6&+(5 c8)%$8 (,1(6 ectuOg;3(5,0(176P f$6 f,$*5$00 =(,*7 (,1( 7*(1 0,7 415 JTN UK 81' '(0 n25(17=O)?50,*(1 5(621$17(1 v(,/ JVK '(5 u86=(37,%,/,7>7 UP q5'181* 4JUK =86$00(1P J%K d(5(&+1(7( J6 6 6 6K 81' *(0(66(1( JAAK ectuOu3(.75(1 921 02/(.8/$5(0 u7,&.6725 )@5 9(56&+,('(1( v(03(5$785(1P
|85 v(03(5$785O 81' m21=(175$7,216%(67,0081* :(5'(1 ',( ectuOu3(.75(1 6,O 08/,(57P f$%(, :,5' ',( %(*5(1=7( 63(.75$/( c89?681* '(5 p$&+:(,6$33$5$785 '85&+ h$/781* '(6 7+(25(7,6&+(1 ectuOu3(.75806 0,7 (,1(5 c33$5$7()81.7,21 ,1 h250 (,1(6 x2,*7Or527/6 %(5@&.6,&+7,*7P f,( r$5$0(7(5 '(5 x2,*7Oh81.7,21 :(5'(1 @%(5 ',( %(670?*/,&+( %(5(,167,0081* =:,6&+(1 (,1(0 (;3(5,0(17(//(1 81' %(5(&+1(O 7(1 u3(.7580 (50,77(/7P d(, *(5,1*(1 m21=(175$7,21(1 %(*5(1=7 '(5 1,&+75(621$17( c17(,/ 415 Ji/P JUPXVKK ',( (55(,&+%$5( p$&+:(,6(0371'/,&+.(,7P
Temperaturabweichung/K
0 -50
-100
-150 0 60 20 40 80 Abstand vom Thermoelement/mm
100
c%%P UPSZ g,19866 '(5 v(03(5$7850(6681* 0,7 v+(502(/(0(17(1 $8) ',( /2.$/( h/$00(1O 7(03(5$785N ',( %(5@+581*6)5(, 0,7 ectu *(0(66(1 :85'( LUWbP
UPU n$6(563(.7526.23,( 921 x(5%5(1181*6352=(66(1
UU[
k0 i(*(16$7= =8 '(1 /$6(5237,6&+(1 v(03(5$7850(6681*(1 67?5(1 u21'(1 J=P dP v+(502(/(0(17(K ',( (0371'/,&+( 5($.7,9( u75?081* ,1 (,1(5 h/$00(P u,( 9(5>1O '(51 1,&+7 185 ',( /2.$/(1 u75?081*6*(6&+:,1',*.(,7(1N 621'(51 9(5856$&+(1 $8&+ g1(5*,(75$16)(5 '85&+ u75$+/81* 81' y>50(/(,781* 62:,( .$7$/5(1 Jc%%P UPS[KP f(5 c%67$1' '(5 i,77(5O /,1,(1 J%=:P i,77(5(%(1(1K W 3 + B JT 6,1)K (5*,%7 6,&+ $86 '(5 y(//(1/>1*( + 81' '(0 y,1.(/ T )N '(1 ',( r803675$+/(1 %,/'(1P k16*(6$07 .$11 0$1 '5(, i,77(571*( + :,5' '$11 817(5 '(0 d5$**Oy,1.(/ ad J0,7 6,1ad 3 + B JT MKK *(675(87P h@5 '(1 |(5)$// '(5 v(03(5$78502'8/$7,21 6,1' f,586,21 81' y>50(/(,781*N )@5 ',( f>03)81* '(5 $.867,6&+(1 y(//( ',( x,6.26,7>7 '(6 o(',806 9(5$17:257/,&+P d(, x(5:(1'81* 81O 7(56&+,('/,&+(5 y(//(1/>1*(1 )@5 r803O 81' r52%(675$+/(1 635,&+7 0$1 921 /$6(5O ,1'8=,(57(5 7+(50,6&+(5 i,77(563(.7526.23,( JnkviuKP f,(6 (5/$8%7 =P dP ',( f(7(.O 7,21 921 1,&+79825(6=,(5(1'(1 m2+/(1:$66(56725(1 '85&+ 02/(.@/63(=,76&+( c1O 5(*81* 0,7 $%67,00%$5(1 k1)5$527/$6(51 81' '(1 p$&+:(,6 ,0 (;3(5,0(17(// (,1O )$&+(5(1 6,&+7%$5(1 2'(5 1$+O,1)5$527(1 u3(.75$/%(5(,&+ LUXbP k0 i(*(16$7= =8 nkh
Schreibstrahl
∆=
λ 2 sin Θ
Lesestrahl
2Θ Schreibstrahl
Signalstrahl
c%%P UPS[ k17(535(7$7,21 '(5 u,*1$/(1767(+81* %(, fhyo ,1 (,1(5 62 *(1$117(1 3+$6(1.21O -8*,(57(1 c125'181* J6P c%%P UPSXK '85&+ d(8*81* '(6 n(6(675$+/6 $1 '(0 '85&+ ',( k17(5O )(5(1= '(5 %(,'(1 u&+5(,%675$+/(1 ,1'8=,(57(1 237,6&+(1 i,77(5P
UVR
U x(5%5(1181*
,67 %(, nkviu ',( 5$6&+( n?6&+81* '(5 $1*(5(*7(1 |867>1'( 921 x257(,/] nkviu ,67 '$+(5 ,16%(621'(5( )@5 o(6681*(1 %(, +2+(0 f58&. *((,*1(7P u&+/,(M/,&+ .?11(1 r2/$5,6$7,216*,77(5 (1767(+(1N :(11 ',( %(,'(1 r803675$+/(1 *(.5(8=7( r2/$5,6$O 7,2165,&+781*(1 $8):(,6(1P f,( 63(.75$/ ,17(*5,(57( fhyoOu,*1$/,17(16,7>7 .$11 )@5 (,1 |:(,Op,9($8Ou76$%O +>1*,*.(,7 '(6 fhyoOu,*1$/6 .$11 '85&+ (,1 c5%(,7(1 ,0 *(6>77,*7(1 d(5(,&+ k35 . T k6$7 5('8=,(57 :(5'(1P d(, x(5:(1'81* (,1(5 3+$6(1.21-8*,(5(1'(1 u75$+/*(2O 0(75,( J6P c%%P UPSXKN %(, '(5 x25:>576O 81' t@&.:>5763803675$+/ ,1 (17*(*(1*(O 6(7=7(5 t,&+781* /$8)(1N .$11 ',( f233/(59(5%5(,7(581* ,0 fhyoOu,*1$/ 9(50,(O '(1 :(5'(1 Jc%%P UPTRKP
80
O12(10) O12(11)
Intensität/w.E.
60
O12(12)
LIF
40 DFWM
20
0
51.7
51.8
51.9 52.0 Frequenz _ 44000/cm-1
52.1
52.2
52.3
c%%P UPTR f233/(5)5(,( u3(.7526.23,( 0,7 fhyo\ x(5*/(,&+ '(5 nkhO 81' fhyoOu3(.7O 5(1 ,0 cT H A zT GJRNRK %(5*$1* 921 pqP
UPU n$6(563(.7526.23,( 921 x(5%5(1181*6352=(66(1
UVS
UPUPTPU r2/$5,6$7,21663(.7526.23,( d(, '(5 5(621$17(1 y(&+6(/:,5.81* (,1(6 =,5.8/$5 32/$5,6,(57(1 .2+>5(17(1 r803O 675$+/6 .$11 ,1 (,1(0 o2/(.@/(16(0%/( (,1( $1,627523( x(57(,/81* Jq5,(17,(581*K ,1'8=,(57 :(5'(1N 'P +P ',( |867>1'( '(5 (17$57(7(1 0$*1(7,6&+(1 s8$17(1=$+/(1 '(6 i581'O %=:P $1*(5(*7(1 |867$1'(6 :(5'(1 1,&+7 */(,&+0>M,* NN(179?/.(57DDN 62 '$66 ',( r52-(.7,21(1 '(5 f5(+,038/69(.725(1 ,1 (,1( $86*(=(,&+1(7( t,&+781* =(,O *(1 81' ',( t27$7,216%(:(*81*(1 '(5 o2/(.@/( (,1( )(67( r+$6(1%(=,(+81* $8)O :(,6(1P f85&+ (/$67,6&+( u7?M( .$11 ',(6( c1,627523,( :,('(5 5(/$;,(5(1 Jt(25,(1O 7,(581*KP f,( c1,627523,( :,5' 0,7+,/)( (,1(6 r52%(675$+/6 1,('5,*(5 k17(16,7>7 '(O 7(.7,(57N ,1'(0 '$6 o(6692/80(1 =:,6&+(1 =:(, *(.5(8=7(1 r2/$5,6$725(1 326,7,2O 1,(57 :,5'P k1 (,1(5 7+(25(7,6&+(1 d(6&+5(,%81* .$11 0$1 =(,*(1N '$66 ',( r2/$5,O 6$7,21663(.7526.23,( (%(162 :,( fhyo (,1 x,(5:(//(10,6&+352=(66 ,67N %(, '(0 -('2&+ ',( r2/$5,6$7,2165,&+781*(1 921 r52%(O 81' u,*1$/675$+/ ,00(5 6(1.5(&+7 =8(,1$1'(5 67(+(1 LUYbP h@5 ',( k17(16,7>7 '(6 75$160,77,(57(1 r52%(675$+/6 *,/7\
2
kru 3 kR . 1 )T 1 %T 1
3
(.ST/ ) 1 %; J(.ST/KT S 1 P T S 1 ;T SX S 1 ;T
JUPXYK
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JUPXZK
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UPUPTPV o(+53+2721(1$%62537,21 81' O,21,6$7,21 f(5 237,6&+( p$&+:(,6 9(56&+,('(1(5 ,1 x(5%5(1181*6352=(66(1 :,&+7,*(5 u3(=,(6 Jy$66(56725O 81' u$8(56725$720(N m2+/(10212;,' 8P $PK *(/,1*7 1,&+7 '85&+ g,1O 3+2721(1$15(*81*N '$ ',( +,(5)@5 127:(1',*(1 y(//(1/>1*(1 ,0 x$.880Owx J+ " TRR 10K /,(*(1 81' ,1 h/$00(1 92//67>1',* $%625%,(57 :(5'(1P f,(6(6 r52%/(0 .$11 0$1 0,7+,/)( '(5 o(+53+2721(1$%62537,21 JorcK 80*(+(1N %(, '(5 r+2721(1 />1*(5(5 y(//(1/>1*(1 =85 c15(*81* (,1*(6(7=7 :(5'(1 .?11(1P f,( %(5*$1*6O :$+56&+(,1/,&+.(,7 y JpK )@5 (,1(1 pOr+2721(1@%(5*$1* 0,7 '(0 c%62537,21648(5O 6&+1,77 1J1K 81' '(1 n$6(5,17(16,7>7(1 k,J6,K ,67 y J1K 3
1J1K kS J6SK P P P k1 J61K P @16S P P P 61
JUPX[K
UVT
U x(5%5(1181* M+
ω1
ω1
IP
ω1
S1 ω1 S0
(a)
ω1
ω1 (b)
ω1 (c)
(d)
ω2
∆t ω 2
ω1
ω1 (e)
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7
T 4w P 0
JUPYRK
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UPV n$0,1$5( 925*(0,6&+7( h/$00(1
UVU
UPV n$0,1$5( 925*(0,6&+7( h/$00(1 UPVPS o$66(163(.7520(75,6&+( o(6681*(1\ o$-25,7>7(163(=,(6 h/$&+( /$0,1$5( h/$00(1 6,1' (,1 :,&+7,*(6 y(5.=(8* =85 g17:,&./81* 81' %(5O 35@)81* 921 x(5%5(1181*602'(//(1 0,7 '(7$,//,(57(5 d(6&+5(,%81* &+(0,6&+(5 t(O $.7,2160(&+$1,60(1P %(5 (,1(5 *(6,17(57(1 o(7$//3/$77(N '85&+ ',( @%(5 (,1(1 s8(56&+1,77 921 0(+5(5(1 |(17,0(7(51 (,1 */(,&+0>M,*(5 u7520 (,1(6 d5(116725B n8)7Oi(0,6&+(6 0,7 .2167$17(0 o,6&+81*69(5+>/71,6 $86675?07N %,/'(7 6,&+ (,1( 6&+(,%(1)?50,*( h/$00(1)5217 $86P k67 '(5 f85&+0(66(5 ',(6(5 h/$00( *52M *(18*N .?11(1 ,1 '(5 o,77( g,19@66( '(5 t$1'%(5(,&+( $86*(6&+/266(1 :(5'(1P f,( m21O =(175$7,2163527/( (17/$1* '(5 =(175$/(1 c&+6( /$66(1 6,&+ '$11 ',5(.7 0,7 '(1 |(,7O 3527/(1 (,1(5 (,1',0(16,21$/(1 u,08/$7,2165(&+181* .255(/,(5(1P d(, *(1@*(1'(0 c%67$1' 921 '(5 h/$00(1)5217 67(//7 6,&+ ',( )@5 ',( -(:(,/,*( h/$00(17(03(5$785 81' d5(11*$6=86$00(16(7=81* 787* %(, p,('(5'58&. J(,1,*( SRU %,6 SRV r$K '85&+*()@+57P w17(5 ',(6(1 d(',1*81*(1 (5675(&.(1 6,&+ ',( i5$',(17(1 '(5 :(6(17/,&+(1 5($.7,9(1 u3(=,(6 @%(5 (,1(1 d(5(,&+ 921 (,1,*(1 o,//,0(7(51 81' 6,1' '$+(5 0,7 02'(51(1 (;3(5,0(17(//(1 v(&+1,.(1 *87 0(66%$5P f,( m21=(175$7,21 '(5 j$83763(=,(6 '(5 x(5%5(1181* .$11 0$66(163(.7526.2O 3,6&+ 817(568&+7 :(5'(1P y,( %(, $//(1 r52%(11$+0(7(&+1,.(1 0866 +,(5 ,1 '(5 u,08/$7,21 $%(5 ',( x(5>1'(581* '(5 w0*(%81*6%(',1*81*(1 '85&+ ',( c1:(6(1O +(,7 '(5 r52%(1621'( %(5@&.6,&+7,*7 :(5'(1P f,( g5*(%1,66( (,1(5 62/&+(1 o(6681* ,1 (,1(5 0,7 c5*21 9(5'@117(1 r523$1Bu$8(56725Oh/$00( J3 3 SRV r$K 6,1' ,1 c%%P UPTT$ '$5*(67(//7 Ju1',* 9(5O 6&+:,1'(7 81' 6,&+ */(,&+=(,7,* J%(, =81(+0(1'(5 v(03(5$785K ./(,1(5( m2+/(1:$6O 6(56725Oh5$*0(17( 81' y$66(56725 %,/'(1N :>+5(1' ',( m21=(175$7,21 '(5 q;,'$O 7,216352'8.7( J=81>&+67 eq 81' jTqK 67(,/ $167(,*7P y>+5(1' ',( jTqOm21=(1O 75$7,21 5$6&+ ,+5(1 i/(,&+*(:,&+76:(57 (55(,&+7N %(1?7,*7 ',( 92//67>1',*( q;,'$7,21 921 eq =8 eqT 0(+5 |(,7P g567 1$&+ (7:$ SR 00 +$%(1 6,&+ ',( +,(5 817(568&+7(1 u3(=,(6 '(1 i/(,&+*(:,&+76.21=(175$7,21(1 $1*(1>+(57P }1'(581*(1 '(5 i$6=8O 6$00(16(7=81* %(, *5?M(5(0 c%67$1' =85 h/$00(1=21( *(+(1 $8) '$6 /$1*6$0( c%.@+/(1 '(6 c%*$6*(0,6&+6 =85@&.P p(%(1 '(1 +,(5 $8)*()@+57(1 u3(=,(6 .?11(1 0,7 (,1(5 c1/$*(N :,( 6,( ,1 c%%P UPTT% 6.,==,(57 ,67N (,1( x,(/=$+/ 817(56&+,('/,&+(5 o2/(.@/(N :,( 6,( %(,63,(/6O :(,6( $/6 t8M925/>8)(5 ,1 %5(1167255(,&+(1 h/$00(1 $8)75(7(1N 48$17,7$7,9 %(O 67,007 :(5'(1 LVbP k1 '(0 @%(5 ',( u21'( $86 '(5 h/$00( (;75$+,(57(1 i$6*(0,6&+
UVV
U x(5%5(1181* Brenngas H2O
20
CO
10
Molenbruch /%
CO2
Brenner
O2
5 H2 2
Flamme Turbopumpe 10-5 mbar
OH
C2H4
1
zur Pumpe (50 mbar)
beweglich
N2
50
±10 %
Düse Skimmer
Flugzeitmassenspektrometer (Reflektron) Detektor
0.5
Turbopumpe 10-7 mbar
C3H8
0.2 0.1 (a)
0
5 z/mm
10
Anregungslaser (b)
Turbopumpe 10-6 mbar
Ionisationslaser
c%%P UPTT J$K u758.785 (,1(5 /$0,1$5(1 925*(0,6&+7(1 r523$1Bu$8(56725Oh/$00( J9(5'@117 0,7 c5*21K ,1 c%+>1*,*.(,7 920 c%67$1' =85 d5(11(52%(59>&+( J%(, 3 3 SRV r$KP J%K tgorkO c8)%$8 =85 0$66(163(.7520(75,6&+(1 w17(568&+81* '(5 i$6=86$00(16(7=81* ,1 '(5 h/$00( Jc7$.$1 LVbKP
:(5'(1 @%(5 5(621$17( o8/7,3+2721(1,21,6$7,21 JtgorkK (,1=(/1( o2/(.@/./$66(1 *(=,(/7 ,21,6,(57 81' ,0 1$&+*(6&+$/7(7(1 h/8*=(,70$66(163(.7520(7(5 1$&+ ,+5(5 o$66( *(75(117 '(7(.7,(57P k0 tgorkOr52=(66 :,5' '$%(, n$6(5675$+/81* (,1*(6(7=7N ',( ',( *(:@16&+7(1 o2/(.@/( =81>&+67 '85&+ 5(621$17( c%62537,21 ,1 (,1(1 $1O *(5(*7(1 (/(.7521,6&+(1 |867$1' 9(56(7=7N $86 '(0 +(5$86 '85&+ c%62537,21 :(,7(5(5 r+2721(1 k21,6$7,21 67$7771'(7 J6P c%6&+1P UPUPTPVKP f,( '233(/7( u(/(.7,9,7>7 Jc1O 5(*81*6:(//(1/>1*( 81' o2/(.@/0$66(K (5/$8%7 ',( 6(/(.7,9( f(7(.7,21 NN>+1/,&+(5DDN $%(5 )@5 ',( c8)./>581* %(,63,(/6:(,6( '(5 t($.7,2160(&+$1,60(1 ,1 '(5 t8M%,/O '81* (176&+(,'(1'(5 o2/(.@/( J=P dP k620(5(K 0,7 *52M(5 v5(116&+>5)(P
UPVPT n$6(5237,6&+( o(6681*(1\ o,125,7>7(163(=,(6 81' t$',.$/( |$+/5(,&+( u3(=,(6 (17=,(+(1 6,&+ :(*(1 ,+5(5 *(5,1*(1 m21=(175$7,21 Jo,125,7>O 7(163(=,(6K 2'(5 ,+5(5 +2+(1 t($.7,9,7>7 Jt$',.$/(K '(1 2%(1 *(1$117(1 o(669(5O )$+5(1P |8'(0 ,67 ,1 9,(/(1 u,78$7,21(1 (,1( %(5@+581*6/26( o(6681* :@16&+(16O :(57N '$ ,1 '$6 u75?081*6)(/' (,1*(%5$&+7( u21'(1 ',( i(20(75,( '(6 r52%/(06 ,1 81@%(56,&+7/,&+(5 y(,6( 9(5>1'(51 81' ',( u21'(12%(59>&+( '85&+ y>50(@%(575$* 81' .$7$/7 ',( t($.7,21 67?57P k1 62/&+(1 h>//(1 .200(1 /$6(523O 7,6&+( x(5)$+5(1 =80 g,16$7= J6P c%6&+1P UPUKP f,( y(&+6(/:,5.81* 921 u7,&.6725 0,7 '(5 h/$00(1&+(0,( ,67 921 %(621'(5(0 k17(5(66(N '$ pq Ju7,&.67252;,'K (,1 :(6(17/,&+(5 '85&+ x(5%5(1181*6352=(66( )5(,*(6(7=7(5 u&+$'6725 ,67P u2:2+/ )@5
UPV n$0,1$5( 925*(0,6&+7( h/$00(1
UVW
0.10
0.01
0.05
0
0
4
2000
2
1000
0
Teilchendichte/ Teilchendichte/ 1012 cm-3 1011 cm-3
(a)
(b)
0
5 10 15 Abstand zum Brennerkopf/mm
20
0
Molenbruch von OH
0.02
Temperatur/K
Teilchendichte Molenbruch von NO/1015 cm-3 von CH3
',( d,/'81* $/6 $8&+ )@5 '(66(1 |(567?581* JNNpqO5(%851DDK ,11(5+$/% '(5 h/$00( 6,1' t($.7,21(1 0,7 ejUON ejO 81' epOt$',.$/(1 921 *52M(5 d('(8781*P f,( w17(568&+81* ',(6(5 u3(=,(6 ,1 p,('(5'58&.9$00(1 J+,(5 ejVBpqBqTBpTOh/$0O 0(1K ,67 (,1 77(163(=,(6P f,( ,1 c%%P UPTU '$5*(67(//7(1 ejUON qjO 81' pqOm21=(175$7,2163527/( 6,1' @%(5 $%62537,21663(.7526.23,6&+( o(6681*(1 %(67,007 :25'(1P f,( 5(/$7,9( c%O 62537,21 '(5 c15(*81*6:(//(1/>1*( ,67 $8)*581' '(5 *(5,1*(1 i5?M( '(5 h/$00( J:(1,*( &0K *(5,1*P |85 x(567>5.81* '(6 o(666,*1$/6 :,5' '$+(5 @%(5 u3,(*(/ '(5 n$6(5675$+/ 0(+5(5( o$/( '85&+ ',( h/$00( *(/(,7(7N %(925 (5 $8) '(1 f(7(.725 )>//7P f(5 x(5*/(,&+ '(5 v5$160,66,21 '(5 h/$00(1*$6( %(, c%67,0081* '(5 n$O 6(5:(//(1/>1*( $8) %=:P $%6(,76 '(5 5(621$17(1 c%62537,21 (5/$8%7 A 817(5 d(5@&.O 6,&+7,*81* '(5 /2.$/(1 v(03(5$785 A ',( 48$17,7$7,9( d(67,0081* '(5 m21=(175$O 7,21P c167(//( '(5 x(5/>1*(581* '(5 c%62537,216675(&.( />667 6,&+ =85 o(6681* *(O 5,1*(5 c%62537,21(1 (,1( x$5,$17( $1:(1'(1N ',( 62 *(1$117( e$9,77(1Ou3(=,(6 ,1 ejVBqTBpqBpTOp,('(5'58&.O 9$00(1P ejUN qjN pq 81' ',( v(03(5$785 6,1' $%62537,21663(.7526.23,6&+ *(0(66(1 LUbP f,( x(57(,/81* 921 ej 81' ep ,67 @%(5 nkh %(67,007 81' 0,7 etf .$/,%5,(57 J6P c%%P UPTV LUZbKP
U x(5%5(1181* Raumfilter
Farbstofflaser oder OPO
Flamme Kamera
Nd:YAG-Laser
Brenner
Detektor
(a)
Computer
Oszilloskop
CH-Teilchenzahldichte/1012cm-3
0
0.25
0.50
0.75
1.00
1.25
1.50 1.50 1.00 0.50
-3
-2
-1
CN-Teilchenzahldichte/1011cm-3
0
0
1
2
3
0.25
0.50
0.75
1.00
0
1.25 1.50 1.00
Abstand zum Brennerkopf
UVX
0.50 0 -3 (b)
-2
-1
0
1
2
3
Brennerkopf
c%%P UPTV J$K u&+(0$7,6&+(5 c8)%$8 '(5 6,08/7$1(1 o(6681* 921 o,125,7>7(163(=,(6Om21O =(175$7,2169(57(,/81*(1 0,7 nkh 81' etf LUZbP f,( %(,'(1 u3,(*(/ 925 81' +,17(5 '(5 h/$00( %,/'(1 '(1 t(621$725N ',( |(,7$%+>1*,*.(,7 '(6 '85&+ '(1 925'(5(1 u3,(*(/ $8675(7(1'(1 n,&+76 75>*7 ',( J$%62/87(K m21=(175$7,216,1)250$7,21P c86 '(5 6,08/7$1(1 nkhOo(6681* :,5' ',( 5(/$7,9( m21=(175$7,2169(57(,/81* (17/$1* '(6 n$6(5675$+/6 %(67,007 81' '$6 c%62537,216O 6,*1$/ $8) c%:(,&+81*(1 921 '(5 c11$+0( (,1(5 NN9$&+(1DD h/$00( .255,*,(57P J%K |:(,',O 0(16,21$/( ejO 81' epOnkhOm21=(175$7,2169(57(,/81*P
t(9(;,216*5$' 921 77 '(5 u3,(*(/ %(67,007] '(5 (,1*(.233(/7( n$6(5,038/6 ./,1*7 $/62 185 /$1*6$0 $%P c%625%,(57 '$6 o(',80 ,11(5+$/% '(6 t(9(.7256 '85&+ c%67,00(1 '(5 u75$+/81* $8) (,1( o2/(.@/5(621$1=N 1,007 '$*(*(1 ',( i@7( '(6 t(621$7256 67$5. $%P g,1(
UPV n$0,1$5( 925*(0,6&+7( h/$00(1
UVY
m21=(175$7,2160(6681* ,67 '$+(5 0?*/,&+N :(11 0$1 ',( |(,7$%+>1*,*.(,7 '(5 J6(+5 *(5,1*(1K n,&+7,17(16,7>7 %(2%$&+7(7N ',( '(1 t(621$725 '85&+ (,1(1 '(5 u3,(*(/ 9(5/>667P f,(6(6 x(5)$+5(1 :85'( %(, '(1 ejO 81' epOo(6681*(1N ',( ,1 c%%P UPTU% '$5O *(67(//7 6,1'N (,1*(6(7=7N 80 ',( nkhOo(6681*(1 J6P c%6&+1P UPUPSPTK =8 .$/,%5,(5(1P f,( (17/$1* '(6 ,0 t(621$725 NN(,1*()$1*(1(1DD n$6(5675$+/6 (0,77,(57( nkhOk17(1O 6,7>7 :85'( '85&+ (,1( m$0(5$ 0,7 (,1',0(16,21$/(5 q576$89?681* '(7(.7,(57P f,( g5*(%1,66( $86 817(56&+,('/,&+(1 o(66326,7,21(1 2%(5+$/% '(6 d5(11(5.23)(6 :85O '(1 '$11 =8 '(1 ,1 c%%P UPTV% *(=(,*7(1 =:(,',0(16,21$/(1 d,/'(51 =86$00(1*(O )@*7P g6 =(,*7 6,&+N '$66 ',( c11$+0( (,1(5 NN9$&+(1DD h/$00( 1,&+7 *(5(&+7)(57,*7 ,67P c8)*581' 921 t$1'(5(.7(1 (5*,%7 6,&+ (,1( 6&+:$&+( y?/%81*N ',( :,('(580 %(, '(5 c1$/7(163(=,(6 ,0 68%O330O d(5(,&+P
UPVPU u3(.7526.23,6&+( w17(568&+81*(1 ,1 j2&+'58&.9$00(1 o,7 =81(+0(1'(0 f58&. 1,007 ',( f,&.( '(5 h/$00(1)5217 $%P g,1( '(7$,//,(57 $8)*(/?67( o(6681* '(5 m21=(175$7,2169(57(,/81*(1 ,11(5+$/% '(5 h/$00(1)5217 ,67 '$+(5 1,&+7 0(+5 0?*/,&+P k1 /$0,1$5(1 h/$00(1 %(6&+5>1.(1 6,&+ ',( o(6O 681*(1 817(5 j2&+'58&.%(',1*81*(1 $8) ',( c%*$6=21(P f(112&+ 6,1' o(6681*(1 817(5 ',(6(1 d(',1*81*(1 ,17(5(66$17N '$ (,1 *52M(5 v(,/ 7(&+1,6&+(5 x(5%5(1181*6O
achromatisches Objektiv
Laserlinienbreite (0.5 cm-1)
Filter
Hochdruckbrenner zylindrisches Teleskop
Spektrometer Photodiode
frequenzverdoppelter Farbstofflaser
Fluoreszenzintensität/w.E.
ICCD Kamera
40325
1 bar 5 bar 10 bar 30 bar 80 bar
40330 40335 Wellenzahl/cm-1
40340
c%%P UPTW u3(.7526.23,6&+( w17(568&+81* ,1 j2&+'58&.9$00(1P J$K u&+(0$ '(6 (;3(5,O 0(17(//(1 c8)%$86P J%K n,1,(19(5%5(,7(581* 81' x(5/867 '(5 t27$7,216)(,16758.785 0,7 =81(+O 0(1'(0 f58&. $0 d(,63,(/ 921 pqP
UVZ
U x(5%5(1181*
352=(66( J=P dP ,1 o2725(1 81' h/8*=(8*75,(%:(5.(1K 817(5 (5+?+7(0 f58&. $%/>8)7N :2%(, ',( y$+56&+(,1/,&+.(,7 921 f5(,(5672M5($.7,21(1 67(,*7N ',( ,1 p,('(5'58&.O 9$00(1 185 (,1( 817(5*(25'1(7( t2//( 63,(/(1P |80 $1'(5(1 (50?*/,&+(1 '(5$57,*( h/$00(1 ',( g17:,&./81* 81' e+$5$.7(5,6,(581* 921 63(.7526.23,6&+(1 o(7+2O '(1N ',( $16&+/,(M(1' *((,*1(7 6,1'N $8&+ ,1 7(&+1,6&+(1 r52=(66(1 48$17,7$7,9( m21O =(175$7,216,1)250$7,21(1 =8 /,()(51P f,(6( 63(.7526.23,6&+(1 c1)25'(581*(1 62//(1 $0 )2/*(1'(1 d(,63,(/ .85= *(O 6&+,/'(57 :(5'(1P o,7 =81(+0(1'(0 f58&. 1,007 ',( d5(,7( '(5 c%62537,216/,1,(1 '(5 u3(=,(6 '85&+ f58&.9(5%5(,7(581* 67$5. =8 J6,(+( c%6&+1P UPUPSPSKP f,(6 ,67 ,1 c%%P UPTW% $1+$1' 921 pqOnkh ,0 f58&.%(5(,&+ 921 SAZR %$5 '$5*(67(//7P f,(6( n,1,(19(5%5(,7(581* 75,77 1,&+7 185 %(, '(5 o2/(.@/6257( $8)N ',( 817(568&+7 :(5'(1 62//N 621'(51 $8&+ %(, $1'(5(1 o2/(.@/(1N ',( %(, >+1/,&+(1 g1(5*,(1 (/(.7521,6&+( %(5*>1*( $8):(,6(1P f,( c%62537,21663(.75(1 %(*,11(1 6,&+ '$+(5 =8 @%(5/$33(1P f$'85&+ 1,007 ',( v5(116&+>5)( '(5 c15(*81* $%N 81' (6 0866 1$&+ *((,*1(7(1 63(.75$/(1 u&+(0$7$ J%(=@*/,&+ c15(*81*6:(//(1/>1*( 81' f(7(.7,216%(5(,&+K *(O 68&+7 :(5'(1N ',( $8&+ 817(5 j2&+'58&.%(',1*81*(1 (,1( +2+( u(/(.7,9,7>7 *(:>+5O /(,67(1 81' 620,7 $8&+ ,1 7(&+1,6&+(1 j2&+'58&.666,*( g5*(%1,66( /,()(51P
UPVPV |@1'352=(66( f,( h5$*(N 2% (,1( d5(116725Bu$8(56725Oo,6&+81* 817(5 %(67,007(1 v(03(5$785O 81' f58&.%(',1*81*(1 63217$1 =@1'(7 2'(5 $%(5 ,1 '(5 n$*( ,67N (,1( x(5%5(1181* =8 817(5+$/7(1N %=:P :(/&+(5 g1(5*,((,175$* )@5 (,1( |@1'81* (,1(6 0(7$67$%,/(1 i(0,6&+(6 (5)25'(5/,&+ ,67N ,67 62:2+/ )@5 ',( 7(&+1,6&+( p87=81* '(5 x(5%5(1181* $/6 $8&+ )@5 ',( u,&+(5+(,767(&+1,. 921 =(175$/(5 d('(8781*P |:(, 817(56&+,('/,&+( r52=(66( 6,1' '$)@5 (176&+(,'(1'P |80 (,1(1 0866 ',( t$',.$/5($.7,21 ,1 i$1* *(+$/7(1 :(5'(1N 'P +P (6 0@66(1 0,1'(67(16 62 9,(/( t$',.$/( @%(5 m(77(19(5=:(,O *81*65($.7,21(1 1(8 *(%,/'(7 :(5'(1 :,( '85&+ y$1'(5(.7( %=:P m(77(1$%%58&+O t($.7,2166&+5,77( 9(51,&+7(7 :(5'(1P |80 $1'(5(1 0866 6,&+(5*(67(//7 6(,1N '$66 ',( x(5%5(1181* 0,1'(67(16 62 9,(/ y>50( )5(,6(7=7N :,( '85&+ y>50(75$163257 1$&+ $8M(1 $%*()@+57 :,5'P f,(6( %(,'(1 i581'%(',1*81*(1 )@+5(1 =8 '(1 ,1 c%%P UPTX $0 d(,63,(/ '(5 m1$//O *$65($.7,21 JjTBqTK '$5*(67(//7(1 |@1'*5(1=(1P f(5 817(5( m859(17(,/ J(567( |@1'O *5(1=(K :,5' '85&+ '(1 t$',.$/+$86+$/7 '20,1,(57P d(, *(5,1*(0 f58&. ,67 ',( )5(,( y(*/>1*( '(5 o2/(.@/( 62 *52MN '$66 ',( y$+56&+(,1/,&+.(,7 '(5 t$',.$//?6&+81* '85&+ y$1'67?M( *5?M(5 $/6 ',( '(5 m(77(19(5=:(,*81* ,67P g,1( t($.7,21 ,67 '$+(5 185 %(, v(03(5$785(1 0?*/,&+N %(, '(1(1 '85&+ ',( x(5=:(,*81*65($.7,21 JUPYSK $865(,&+(1' t$',.$/( J'$6 81*(3$$57( g/(.7521 '(6 t$',.$/6 ,67 '85&+ '(1 r81.7 6 61*,*.(,7 80.(+57N '20,1,(57 '(5 2%(1 *(1$117( 7+(5O 0,6&+( c63(.7P d(, 6(+5 +2+(0 f58&. :,5' ',( 92/80(1%(=2*(1( g1(5*,()5(,6(7=81* 62 +2&+N '$66 ',( y>50( 1,&+7 0(+5 0,7 '(5 (5)25'(5/,&+(1 i(6&+:,1',*.(,7 $1 ',( w0*(%81* $%*()@+57 :(5'(1 .$11P g6 .2007 =85 7+(50,6&+(1 g;3/26,21P k67 ',( '$'85&+ (1767(+(1'( t($.7,21 62 +()7,*N '$66 ',( 7(03(5$785O 81' 5($.7,216%(',1*7( x2/80(1=81$+0( 1,&+7 '85&+ v(,/&+(175$163257 .203(16,(57 :(5'(1 .$11N 75(7(1 /2.$/( f58&.*5$',(17(1 $8)P d,/'(7 6,&+ (,1( u72M:(//(N ',( :>+5(1' ,+5(5 c86%5(,O 781* '85&+ $',$%$7,6&+( m2035(66,21 $8)*(+(,=7(6 i$6*(0,6&+ =85 |@1'81* %5,1*7N 9(5856$&+7 ',(6( '(1 %(5*$1* =85 f(721$7,21P k0 i(*(16$7= =85 /$1*6$0(1N '85&+ ',( t$',.$/&+(0,( *(67(8(57(1 h/$00(1)5217$86%5(,781* Jf(9$*5$7,21K 0,7 i(O 6&+:,1',*.(,7(1 ,1 '(5 i5?M(125'181* 921 RPS A SR 0B6 J',( *5?M(5( c86%5(,781*6O *(6&+:,1',*.(,7 *,/7 )@5 785%8/(17( h/$00(1KN :,5' %(, '(5 f(721$7,21 ',( h/$0O 0(1$86%5(,781* '85&+ ',( h25739$1=81*6*(6&+:,1',*.(,7 '(5 f58&.:(//( %(67,007P c8)*581' '(5 +2+(1 u&+$//*(6&+:,1',*.(,7 ,1 +(,M(1 i$6(1 .$11 ',(6 0,7 i(6&+:,1O ',*.(,7(1 %,6 @%(5 SRRR 0B6 (5)2/*(1P y>+5(1' ',( 7+(50,6&+( g;3/26,21 810,77(/%$5 (,16(7=7N :(11 ',( '$=8 (5)25'(5O /,&+(1 x25$866(7=81*(1 *(0>M c%%P UPTX (55(,&+7 :(5'(1N 75,77 ',( t($.7,21 ,0 921 '(5 t$',.$/&+(0,( '20,1,(57(1 d(5(,&+ 0,7 (,1(5 *(:,66(1 x(5=?*(581*N '(5 62 *(O 1$117(1 |@1'9(5=8*6=(,7 2N (,1P y>+5(1' ',(6(5 |(,7 /$8)(1 )@5 ',( x(5%5(1181* (176&+(,'(1'(N ',( |$+/ '(5 )5(,(1 t$',.$/( 9(5*5?M(51'( t($.7,21(1 $%N ',( $%(5 ',( v(03(5$785 '(5 t($.7,2160,6&+81* 185 *(5,1* %((,19866(1P f,( c%1$+0( 921 2 0,7 67(,*(1'(5 v(03(5$785 Ji/P JUPYUKK 5(9(.7,(57 ',( v(03(5$785$%+>1*,*.(,7 J*(O
1000 langsame Reaktion
p/mbar
100 Explosion 10 langsame Reaktion 1
c%%P UPTX
750
T/K
800
850
|@1'*5(1=(1 ,0 jTBqTOuM '(0 c55+(1,86Oi(6(7=N 6P i/P JUPTYKK '(5 =8*581'( /,(*(1'(1 g/(0(17$55($.O 7,21(1P d
2 . c (v P
JUPYUK
d(, m2+/(1:$66(56725(1 75,77 ,0 d(5(,&+ '(5 '5,77(1 |@1'*5(1=( '$6 h(/' '(5 62 *(1$117(1 NN.$/7(1 h/$00(1DD $8)P o,7 =81(+0(1'(5 v(03(5$785 9(56&+,(%7 6,&+ '$6 i/(,&+*(:,&+7 (,1(5 )@5 ',( m(77(19(5=:(,*81* J81' 620,7 )@5 '(1 w17(5+$/7 '(5 x(5%5(1181*K 9(5$17:257/,&+(1 t($.7,21 JUPYV%K =8 '(1 g'8.7(1P |81(+0(1'( y>50()5(,6(7=81* NN%5(067DD $/62 =81>&+67 ',( t($.7,21P eTjX 1 qT S 6e j 1 jqT J$K J M 6e j + eTjWq6T J%K 1 qT J M eTjWq6T 1eTjX S eTjWqqj 1 6eTjW J& K eTjWqqj S eTjW q6 1 6qj J'K JUPYVK n$6(5(;3(5,0(17( *(67$77(1 (,1( '(7$,//,(57( w17(568&+81* 921 |@1'352=(66(1P j,(5O %(, .$11 ',( v(03(5$7859(57(,/81* 81' ',( x(57(,/81* 5($.7,9(5 u3(=,(6 J=P dP '(6 qjOt$',.$/6K 0,7 /$6(5',$*1267,6&+(1 x(5)$+5(1 0,7 +2+(5 5>80/,&+(5 81' =(,7/,&+(5 c89?681* 817(568&+7 81' ',( )@5 ',( |@1'81* 127:(1',*( |@1'(1(5*,( @%(5 c%O 62537,21 921 n$6(5675$+/81* '(71,(57 ,1 '$6 u+5(1' '(5 |@1'81* %,/O '(1'( qj .$11 0,7 +2+(5 =(,7/,&+(5 81' 5>80/,&+(5 c89?681* @%(5 nkh %(2%$&+7(7 :(5'(1P f,( 6,08/7$1( c15(*81* '(6 qjOt$',.$/6 0,7 =:(, y(//(1/>1*(1 (50?*O CO2-Laser
KrF-Excimer-Laser λ 2=248.35 nm
HeCdTeDetektor
Photomultiplier Faser
SrF2Fenster
CCD
CCD Bandpassfilter (297 ± 6) nm KrF-Excimer-Laser λ 1=248.45 nm
Quarzzelle CH3OH/O2
Steuerung
Computer
Monitor
c%%P UPTY g;3(5,0(17 =85 w17(568&+81* '(5 7+(50,6&+(1 |@1'81* ,1 o(7+$12/Bu$8(56725O o,6&+81*(1P
axiale Position/mm
UPV n$0,1$5( 925*(0,6&+7( h/$00(1
CO2-Laser
0
radiale Position/mm 5 -5 0
UWS
T/K 2750 2350
5
1950 1550
10
1150 15 Experiment
Simulation
CO2-Laser Vorheizung
750 350
c%%P UPTZ |:(,',0(16,21$/( v(03(5$7859(57(,/81* ,1 '(5 =@1'(1'(1 o(7+$12/Bu$8(56725O o,6&+81* J}48,9$/(1=9(5+>/71,6 { 3 RP[N f58&. 3 3 U 6 SRV r$KP J$K g;3(5,0(17(//( d(67,0O 081* '85&+ qjOnkhOv+(5020(75,(P J%K f,5(.7( 180(5,6&+( u,08/$7,21 LUXbP
/,&+7 ',( d(67,0081* '(5 v(03(5$7859(57(,/81* J6P c%6&+1P UPUPSPTKP k1 c%%P UPTZ ,67 '$6 g5*(%1,6 (,1(5 62/&+(1 o(6681* '(5 ',5(.7(1 180(5,6&+(1 u,08/$7,21 J6,(+( c%6&+1P UPWPTK '(6 r52=(66(6 *(*(1@%(5*(67(//7P f,( .21,6&+( h250 '(5 h/$00(1O )5217N ',( 6,&+ 62:2+/ ,0 g;3(5,0(17 $/6 $8&+ ,1 '(5 u,08/$7,21 0,7 6(+5 *87(5 %(5(,167,0081* 71'(7N *(+7 $8) ',( x25+(,=81* '(6 i$6*(0,6&+(6 ,0 d(5(,&+ '(6 n$6(5675$+/6 =85@&.P f,( *(5,1*(1 v(03(5$785817(56&+,('( $8)*581' '(5 c%62537,21 '(6 |@1'/$6(5675$+/6 )@+5(1 '85&+ ',( 67$5.( vOc%+>1*,*.(,7 '(5 |@1'352=(66( =85 c86%,/'81* '(5 %(925=8*7(1 h/$00(1$86%5(,781*65,&+781*P p(%(1 '(0 ,17(502/(.8/$5(1 jOc%675$.7,2166&+5,77 $1$/2* '(5 h250(/1 JUPYV&K 81' JUPYV'K %=:P JUPYW$K 81' JUPYW%K J$K tO"ejTOejTq6T 1 tj S tO"ejTOejTqqj 1 6t J%K tO3ejTOejTqqj S tO"ejTOejTq6 1 6qj JUPYWK .$11 (6 %(, $8&+ =8 ,175$02/(.8/$5(1 jOc%675$.7,2166&+5,77(1 *(0>M i/P JUPYX$K .200(1P f,(6( t($.7,21 ,67 -('2&+ 185 0?*/,&+N :(11 '$6 m2+/(16725$720 ,1 "Or26,7,21 J6,(+( o$5.,(581* " ,1 '(1 h250(/1K 1,&+7 '85&+ u(,7(1.(77(1 %/2&.,(57 ,67P J$K tO"ejTOejTq6T S tO"e6jOejTqqj " 6 J%K tO e jOejTqqj 1 qT S tO"eJqq6KjOejTqqj JUPYXK J&K S S tI 6 1 T jqT6 S S jTqT k1 ',(6(0 h$// 75,77 $167(//( '(6 810,77(/%$5(1 m(77(19(5=:(,*81*66&+5,776 i/P JUPYW$K ',( d,/'81* 921 jTqT $8)N '$6 (567 %(, v(03(5$785(1 @%(5 SRRR m 6(+5 5$6&+ '85&+ g5=(8*81* :(,7(5(5 )5(,(5 t$',.$/( =(5)>//7 81' '$0,7 ',( =:(,7( u78)( '(6 $/6 NN|:(,O 678)(1=@1'81*DD %(.$117(1 r52=(66(6 (,1/(,7(7P d(, g55(,&+(1 ',(6(5 u7$%,/,7>76*5(1=( 1,007 '$11 '(5 t($.7,216806$7= 6&+/$*$57,* =8P k1 o2725(1 )@+57 ',(6 =80 62 *(1$117(1 NNm/23)(1DDP f,( g1(5*,( =85 h5(,6(7=81* '(5 t$',.$/( :,5' '85&+ ',( 921 '(5 x(5%5(1181* 9(5856$&+7( f58&.:(//( J'85&+ $',$%$7,6&+( m2035(66,21K *(/,()(57N '(5 r52=(66 ,67 $/62 (,1( f(721$7,21N ',( 6,&+ 0,7 %(56&+$//*(6&+:,1',*.(,7
UWT
U x(5%5(1181*
)25739$1=7 81' u72M:(//(1 0,7 6(+5 67(,/(0 f58&.$167,(* ,1'8=,(57P f,(6( f58&.O :(//(1 .?11(1 ,0 o2725 =(567?5(5,6&+( y,5.81* (17)$/7(1P f$6 m/23)(1 6(/%67 .$11 '85&+ ./(,1( v(03(5$78598.78$7,21(1 921 TR A UR m J62 *(1$117( NN+27 63276DDN 6P c%6&+1P UPZPVK ,1,7,,(57 :(5'(1P f,( u(/%67=@1'81*61(,*81* (,1(6 m5$)767256 :,5' '85&+ ',( NNq.7$1=$+/DD $1*(*(%(1P u,( ,67 '$6 352=(178$/( o,6&+81*69(5+>/71,6 921 ,62Oq.7$1 81' 1Oj(37$1 ,1 (,1(0 |:(,.20321(17(19(5*/(,&+6.5$)76725P f$6 1O j(37$1 $/6 819(5=:(,*7(5 m2+/(1:$66(56725 1(,*7 $1$/2* =85 2%(1 '$5*(67(//7(1 f,6.866,21 67$5. =85 |:(,678)(1=@1'81*N :>+5(1' ,1 ,62Oq.7$1 JTNTNVOv5,0(7++5(1' ,1 /$0,O 1$5(1 h/$00(1 i(6&+:,1',*.(,7 81' u.$/$5( Jf,&+7(N v(03(5$785 81' m21=(175$O 7,21(1K :2+/'(71,(57( y(57( $11(+0(1N 6,1' 785%8/(17( h/$00(1 '85&+ .217,18,(5O /,&+( h/8.78$7,21(1 '(5 i(6&+:,1',*.(,7 &+$5$.7(5,6,(57N ',( ,+5(56(,76 =8 h/8.78$O 7,21(1 '(5 6.$/$5(1 i5?M(1 )@+5(1 .?11(1P f,(6( h/8.78$7,21(1 :(5'(1 '85&+ y,5O %(/ %(',1*7N ',( '85&+ u&+(5.5>)7( ,1 '(5 u75?081* (1767(+(1P f(5 w06&+/$* (,1(5 /$0,1$5(1 ,1 (,1( 785%8/(17( u75?081* (5)2/*7 %(, (,1(5 &+$5$.7(5,67,6&+(1 t(*O +(,76.5$)7 81' (,1(5 67$%,/,6,(5(1'(1 J2'(5 '>03)(1'(1K x,6.26,7>76.5$)7 :,'(563,(O *(/7P f$%(, 6,1' 0 ',( f,&+7(N 9 ',( i(6&+:,1',*.(,7N , ',( |>+,*.(,7 '(6 %(75$&+7(7(1 h/8,'6 J- 3 ,B0K 81' / (,1( &+$5$.7(5,67,6&+( n>1*( '(6 u1*(16.$/(1 %(, '(5 q576',6.5(7,6,(581* $8)O *(/?67 :(5'(1P f,( 785%8/(17( u75?081* .$11 '85&+ (,1 u3(.7580 921 y,5%(/1 %(6&+5,(%(1 :(5'(1N '(5(1 f,0(16,21(1 6,&+ 71*( (K (5675(&.(1P |85 g5)$6681* $//(5 q5766.$/(1 :(5'(1 '$+(5 ,1 -('(5 t$80',0(16,21 75.( J&K ,1 (,1(5 785%8/(17(1 925*(0,6&+7(1 o(7+$19$00(P
UWV
U x(5%5(1181*
:,( ',( y,5%(/67>5.( ,1 (,1(5 785%8/(17(1 o(7+$19250,6&+9$00(P c1$/2*( (;3(O 5,0(17(//( g5*(%1,66( :(5'(1 %(,63,(/+$)7 )@5 1,&+7O925*(0,6&+7( h/$00(1 ,1 c%6&+1P UPYPSPS 925*(67(//7P |86$00(1)$66(1' />667 6,&+ )(6767(//(1N '$66 ,1 '(1 1>&+67(1 =:$1=,* l$+5(1 (,1( 35$.7,.$%/( 0$7+(0$7,6&+( d(6&+5(,%81* 7(&+1,6&+(5 x(5%5(1181*6352=(66( 185 '$11 0?*/,&+ ,67N :(11 62:2+/ ',( v85%8/(1= $/6 $8&+ ',( &+(0,6&+( t($.7,21 '85&+ 9(5(,1)$&+7(N -('2&+ ,1 ,+5(0 i@/7,*.(,76%(5(,&+(1 ./$5 %(857(,/%$5( o2'(//( %(O 6&+5,(%(1 :(5'(1 .?11(1P
UPWPU i(0,77(/7( g5+$/781*6*/(,&+81*(1 k1 '(5 r5$;,6 ,67 0$1 0(,67 1,&+7 $1 /2.$/(1 81' 020(17$1(1 u758.785(1 ,17(5(66,(57N 621'(51 $1 */2%$/(1N =(,7/,&+ *(0,77(/7(1 g5*(%1,66(1P j,(5)@5 /$66(1 6,&+ =(,7/,&+ *(0,77(/7( g5+$/781*6*/(,&+81*(1 +(5/(,7(1P |(,7/,&+( o,77(/:(57( ,1 1,&+767$7,21>5(1 u/7 0$1 ',( :,&+7,*( d(',1*81*N '$66 )@5 '(1 o,77(/:(57 '(5 u&+:$1O .81*(1 %4A& 3 R *,/7P g,1( %(, x(5%5(1181*6352=(66(1 7M,*N ',( h$95(Oo,77(/81* J',&+7(*(:,&+7(7( o,77(/81*K $/6 :(,7(5(1 o,77(/:(57 (,1=8)@+O 5(1P u,( ,67 )@5 (,1( %(/,(%,*( i5?M( 4 '85&+ i/P JUPYZK *(*(%(1 81' (50?*/,&+7 +>87* (,1( .203$.7(5( u&+5(,%:(,6( '(5 g5+$/781*6*/(,&+81*(1P 4% 3
%04& %=:P %0&4% 3 %04& P %4&
JUPYZK
c1$/2* =8 i/P JUPYYK />667 6,&+ $8&+ ',(6( i5?M( ,1 ,+5(1 o,77(/:(57 81' ',( u&+:$1O .81* $8)63$/7(1\ 4J_N 7K 3 4% J_N 7K 1 4AAJ_N 7K N
JUPY[K
ρ ρ t
c%%P UPUR |(,7/,&+( h/8.78$7,21(1 81' =(,7/,&+( o,77(/:(57( %(, (,1(0 67$7,67,6&+ 1,&+767$O 7,21>5(1 r52=(66P
UPW v85%8/(17( 925*(0,6&+7( h/$00(1
UWW
:2%(, 6,&+ )@5 '(1 o,77(/:(57 '(5 h$95(Oh/8.78$7,21 4AA (%(1)$//6 (5*,%7N '$66 %04AA& 3 RP
JUPZRK
u(7=7 0$1 ,1 ',( f(71,7,21 )@5 ',( h$95(Oo,77(/81* i/P JUPYZK ,1 i/P JUPYYK (,1N 62 />667 6,&+ (,1( d(=,(+81* JUPZSK $%/(,7(1N ',( (,1( w05(&+181* '(6 o,77(/:(57(6 (,1(5 x$5,$%/(1 4 ,1 '(1 h$95(Oo,77(/:(57 (5/$8%7P j,(5)@5 0866 -('2&+ ',( m255(/$7,21 %0A4A& '(5 u&+:$1.81*(1 '(5 f,&+7( 81' '(5 i5?M( 4 %(.$117 6(,1P 4% 3 3
%04& %J%0& 1 0AKJ%4& 14AK& 3 %4& %0&
%%0&%4&& 1 %%0&4A& 1 %0A%4&& 1 %0A 4A& %0&
3%4&1
%0A 4A& P %0&
JUPZSK
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UYU
8000
450
Tl 6000
400
T /K
4000 350
300
2000
d2
0
1
t /ms
2
d 2/µm2
Tc
3
4
0
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UYX
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PentroofFenster
Laser
QuarzRing
Auslassventile Drucksensor
70 mm
Zündkerze
Kolben Spiegel
c%%P UPVW
18 mm
Kolbenfenster
Kamera
Einlassventile
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Ruß (LII)
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=
23 mm
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60
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10
106 104
5
η sp ≈ c 3.35
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lg cXanthan [g/l]
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η sp ~ c [η ] 22
η sp 102
η sp ≈ c 1.27 -1.0
Überlappungsgrenze
2.0 (b)
10-2 10-2
η sp ~c [ η]1.09 10-1
c[η ]
100
101
102
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o,7 MR 3 RPRU[RS /2S 0T 02/2S )@5 g66,*6>85( 81' M& 3 RPRRR WTR /2S 0T 02/2S )@5 & 3 RPS o (5+>/7 0$1 (,1(1 f,662=,$7,216*5$' " 3 RPRSUU 81' '$0,7 (,1( f,662=,$O 7,216.2167$17( m 3 SPZR 6 SR2WP f,( y(57( )@5 M& 67(,*(1 0,7 )$//(1'(5 g66,*6>85(O .21=(175$7,21 & 81' (5*(%(1 ,0 t$+0(1 '(5 h(+/(5*(1$8,*.(,7 ',( */(,&+( f,662O =,$7,216.2167$17( mP
WVR
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
XPUPZ f211$1Or27(17,$/ 81' f,586,216327(17,$/ i5(1=(1 =:(, n?681*(1 817(56&+,('/,&+(5 |86$00(16(7=81* $1(,1$1'(5N 62 .?11(1 $1 '(5 m217$.767(//( r27(17,$/',5(5(1=(1 $8)75(7(1N ',( -( 1$&+ t$1'%(',1*81* $8) =:(, 817(56&+,('/,&+( o(&+$1,60(1 =85@&.=8)@+5(1 6,1'P d(,0 f211$1Or27(17,$/ +$1'(/7 (6 6,&+ 80 (,1 (&+7(6 i/(,&+*(:,&+76327(17,$/P f$6 f,586,216327(17,$/ ,67 '$*(*(1 $8) .,1(7,6&+( x25*>1*( =85@&.=8)@+5(1P y(5'(1 =:(, g/(.752/66,* ,67N 1,&+7 -('2&+ )@5 r2//71,66(1 (5+>/7 0$1 '85&+ )2/*(1'( (,1)$&+( c%/(,781*P u2:2+/ )@5 ',( m$7,21(1 m $/6 $8&+ )@5 ',( c1,21(1 c />667 6,&+ '$6 (/(.752&+(0,6&+( i/(,&+*(:,&+7 0,7 '(0 (/(.752O &+(0,6&+(1 r27(17,$/ ,% )2508/,(5(1 J6P c%6&+1P XPTPTKP h@5 ',( %(:(*/,&+(1 m$7,21(1 m=1 0,7 =1 3 = *,/7 ',( d(=,(+81* ,% mNk 3 ,RmNk 1tv /1$mNk 1= h 3k 3 ,% mNkk 3 ,RmNkk 1tv /1$mNkk 1= h 3kk N JXPWUK ',( 1$&+ (,1)$&+(0 w0)250(1 ',( d(=,(+81* )@5 ',( f211$1Or27(17,$/',5(5(1= 3kk 23k 3 (3f 3
0 1
$ tv /1 mNk =h $mNkk
JXPWVK
(5*,%7P g,1( (17635(&+(1'( d(=,(+81* )2/*7 )@5 ',( c1,21(1 0,7 =2 32= (17635(O &+(1' $ tv /1 cNk P JXPWWK 3kk 23k 3 (3f 32 =h $cNkk
0 1
II
I
-
PΖ p A
Ζ-
A
KΖ+
KΖ+ Membran
ϕI
Ζ-
∆ϕ D
ϕ II
c%%P XPST c86%,/'81* (,1(5 f211$1Or27(17,$/',5(5(1= (3f $1 (,1(5 6(0,3(50($%/(1 o(0O %5$1 0,7 1,&+73(50($%/(1 r2/85(/?681*(1 817(56&+,('/,&+(5 m21=(175$7,21 Jc%%P XPSUKP f,( k21(1 9(568&+(1 '85&+ f,586,21 ',( m21=(175$7,216817(56&+,('( =:,6&+(1 %(,'(1 n?681O *(1 k 81' kk $86=8*/(,&+(1P d(6,7=(1 ',( m$7,21(1 (,1( +?+(5( d(:(*/,&+.(,7N 62 I H
II +
I H
II +
Cl-
Cl-
aI
>
a II
aI
(a)
ϕI
>
a II ∆ϕ d
ϕ II
(b)
c%%P XPSU c86%,/'81* (,1(5 f,586,216327(17,$/',5(5(1= (3' %(, =:(, $1(,1$1'(5*5(1=(1'(1 n?681*(1 817(56&+,('/,&+(5 u$/=6>85($.7,9,7>7 J$k # $kkK $8)*581' '(5 d(:(*/,&+.(,76817(5O 6&+,('( '(5 j1O 81' e/2Ok21(1 J$K =8 d(*,11 '(6 m217$.7(6 81' J%K 1$&+ g,167(//81* 67$O 7,21>5(5 x(5+>/71,66( :>+5(1' '(6 m217$.7(6P
WVT
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
:(5'(1 6,( '(1 c1,21(1 925$86(,/(1 81' '$0,7 ',( n?681* kk 0,7 ./(,1(5(5 m21O =(175$7,21 *(*(1@%(5 n?681* k 326,7,9 $89$'(1P f,( r27(17,$/',5(5(1= (3' 3 3kk 23k (5*,%7 6,&+ '85&+ (,1( (,1)$&+( d(75$&+781* '(5 c5%(,76%(75>*(N ',( 0,7 '(0 h/866 (,1(5 n$'81* 921 S h 921 n?681* k 1$&+ kk 9(5%81'(1 6,1'P f,( (/(.75,6&+( c5%(,7 (5*,%7 6,&+ 1$&+ y(/ 3 (3' h P
JXPWXK
h@5 '(1 v5$16)(5 921 (,1(5 n?681* ,1 ',( $1'(5( ,67 (,1( 26027,6&+( c5%(,7 :260 3 :2601 1:2602 3
01
01
$ $ 7 71 tv /1 kk 2 2 tv /1 kk =1 $k 8=2 8 $k
JXPWYK
=8 /(,67(1P j,(5%(, ,67 =8 %(5@&.6,&+7,*(1N '$66 %(, (,1(0 u75209866 921 S h n$'81* 921 k 1$&+ kk 71 B=1 o2/( m$7,21(1 921 k 1$&+ kk 81' 72 B=2 o2/( c1,21(1 ,1 '(5 80*(.(+57(1 t,&+781* 75$163257,(57 :(5'(1P 71 81' 72 6,1' ',( %(5)@+581*6=$+/(1 '(5 k21(1P o,7 '(5 d(',1*81*N '$66 6,&+ ',( c5%(,76%(75>*( =8 p8// $'',(5(1 Jy(/ 1y260 3 RKN )2/*7 )@5 (,1(1 */(,&+(1 n$'81*6%(75$* '(5 k21(1 =1 3 8=2 8 3 = ',( (,1)$&+( d(=,(+81* (3' 3 3kk 23k 3 JS2T 72K
01
$ tv /1 k $kk =h
JXPWZK
)@5 '$6 f,586,216327(17,$/P h@5 '(1 m217$.7 =:(,(5 u$/=6>85(/?681*(1 0,7 &k 3 RPS o 81' &kk 3 RPRS o (5+>/7 0$1 1$&+ i/P JXPWZK 0,7 71 3 RPZU 81' 72 3 RPSY (3' 3 RPRUZ[ xP f,(6(5 (5+(%/,&+( y(57 ,67 (,1( h2/*( '(5 *52M(1 w17(56&+,('( '(5 d(:(*/,&+.(,7(1 %=:P '(5 %(5O )@+581*6=$+/(1 '(5 j1O 81' e/2Ok21(1P g5 67(,*7 :(,7(5N :(11 6,&+ ',( m21=(1O 75$7,21(1 %(,'(5 n?681*(1 12&+ 67>5.(5 817(56&+(,'(1P j1Ok21(1 +$%(1 >+1/,&+ :,( qj2Ok21(1 (,1( 6(+5 +2+( d(:(*/,&+.(,7 81' '$0,7 (,1( *52M( %(5)@+581*6O =$+/ 71 $8)*581' '(5 p$+25'181* '(6 9@66,*(1 y$66(56P d(, u75209866 (5)2/*7 @%(5 (,1( 5$6&+( w0/$*(581* 921 y$66(56725%5@&.(1%,1'81*(1 (,1 y(,7(55(,&+(1 '(5 k21(1/$'81*(1 67$77 (,1(5 /$1*6$0(1 '85&+ t(,%81* %(+,1'(57(1 o,*5$7,21 Jy$1O '(581* ,0 (/(.75,6&+(1 h(/'K +&+( (,1( (176&+(,'(1'( t2//( 63,(/(1P o$1 817(56&+(,'(7 )2/*/,&+ ',( ,11(5( 81' ',( >8M(5( j(/0+2/7=Ou&+,&+7N '(5(1 c86'(+181* '85&+ ',( i5?M( '(5 .217$.7$'625%,(57(1 k21(1 81' '(5 62/9$7,6,(57(1 k21(1 *(*(%(1 ,67P f85&+ ',( 7+(50,6&+( d(:(*81* :,5' 6,&+ (,1 v(,/ '(5 k21(1 921 '(5 g/(.752'(1O 2%(59>&+( )257%(:(*(1 81' '$0,7 =86>7=/,&+ (,1( ',586( f233(/6&+,&+7 $8)%$8(1N >+1/,&+ '(5 ',586(1 k21(1:2/.( 80 (,1 =(175$/(6 k21 Jc%%P XPSVKP f,( ',586( f233(/6&+,&+7 />667 6,&+ 1$&+ i28< LS[N TRb 81' e+$30$1 LTSb ,1 67$5.(5 c1/(+181* $1 ',( f(%+(581*(1 />667 6,&+ ',( */(,&+( d(=,(+81* =:,6&+(1 '(5 n$'81*6',&+7( 0 81' '(0 r27(17,$/$%)$// (3 +(5/(,7(1 Ji/P JXPUZKKP f,( r2,6O Metall
Metall
Elektrolyt
Elektrolyt hydratisiertes Anion
kontaktadsorbiertes Anion hydratisiertes Kation
ϕ
ϕ ∆ϕ
ζ
(a)
AHS
ξ
Ortskoordinate x
(b)
IHS AHS
ξ
Ortskoordinate x
c%%P XPSV o2'(// '(5 r+$6(1*5(1=( g/(.752'(Bg/(.752/8M(5( j(/0+2/7=Ou&+,&+7 JcjuK 81' (,1(5 0?*/,&+(1 w0.(+5 '(6 r27(17,$/$%)$//6 ,1 '(5 ',586(1 f233(/6&+,&+7P f,( u2/9$7,6,(581* '(5 g/(.752'(12%(59>&+( 81' '(5 *(/?67(1 k21(1 0,7 y$66(5',32/(1 ,67 '$5*(67(//7P
XPV f,( f233(/6&+,&+7 $1 '(5 r+$6(1*5(1=( g/(.752'(Bg/(.752/+1/,&+(5 y(,6( :,( ,1 i/P JXPU[KP f,( f,&.( '(5 ',586(1 f233(/O 6&+,&+7 # (17635,&+7 '(5 g17)(5181*N %,6 =8 '(5 '(5 r27(17,$/63581* $8) SB( 6(,1(6 i(6$07:(57(6 $%*()$//(1 ,67P j,(5)@5 *,/7 (,1( ,'(17,6&+( d(=,(+81* :,( )@5 '(1 t$O ',86 '(5 ',586(1 k21(1:2/.( '(5 f(%&+(13+>120(1(1N ,16%(621'(5( %(, m2//2,'(1 81' '(5(1 u7$%,/,7>7P f$6 'Or27(17,$/ ,67 1$&+ (,1(5 (,1)$&+(1 k17(*5$7,21 @%(5 ',( n$'81*6O ',&+7( ,1 '(5 ',586(1 f233(/6&+,&+7 0,7 '(5(1 i(6$07/$'81* s' 9(5.1@3)7\ ( 32
# # s 3 s P & &R ' & &R o
JXPXTK
|85 y$+581* '(5 g/(.7521(875$/,7>7 ,67 ',(6( n$'81* '(5 n$'81* $8) '(5 g/(.752'(1O %=:P h(67.?53(56(,7( so (17*(*(1*(6(7=7 */(,&+N :(11 0$1 '(1 n$'81*6$17(,/ ,1 '(5 67$55(1 f233(/6&+,&+7 =85 g/(.752'( =>+/7P f,( ',5(5(17,(//( m$3$=,7>7 e' '(5 ',586(1 f233(/6&+,&+7 (5*,%7 6,&+ '85&+ f,)O )(5(17,$7,21 '(5 n$'81* $8) '(5 g/(.752'(16(,7( so 1$&+ '(0 'Or27(17,$/P o,7 '(1 g,16&+5>1.81*(1 '(5 j(5/(,781* ',(6(5 d(=,(+81*(1 :,( %(, '(5 v+(25,( 67$5.(5 g/(.752/5.( k $/6 (,1 /$'81*6*(:,&+7(7(6 m21=(175$7,2160$M =8 6(+(1P k1 (,1(5 S o n?681* +$7 '(01$&+ ',( ',586( f233(/6&+,&+7 (,1( c86'(+181* ,0 d(5(,&+ '(5 k21(15$',(1N 81' 6,( )>//7 '(6+$/% 0,7 '(5 67$55(1 f233(/6&+,&+7 =86$00(1P o,7 $%1(+0(1'(5 m21=(175$7,21 '(+17 6,&+ ',( ',586( f233(/6&+,&+7 (5+(%/,&+ ,1 '(1 g/(.752/+(51N '$0,7 (,1 g/(.7521(175$16)(5 @%(5 v811(/352=(66( 67$7771'(1 .$11P f$ $%(5 (,1 v(,/ '(6 r27(17,$/6 ,1 '(5 6,&+ :(,7 ,1 '(1 g/(.752///7N ,67 (5 )@5 ',( m,1(7,. '(5 f85&+75,7765($.7,21 1,&+7 :,5.6$0P p(%(1 $1'(5(1 i5@1'(1 6(7=7 0$1 ,1 '(5 g/(.752'(1.,1(7,. (,1( *52M( m21=(175$7,21 h5(0'(/(.752/1O *(1P f,( u7$%,/,7>7 921 m2//2,'(1 ,67 (%(1)$//6 921 '(5 c86'(+181* '(5 ',586(1 f23O 3(/6&+,&+7 $%+>1*,*P f,( v(,/&+(1 (,1(6 m2//2,'6 :(5'(1 '85&+ (,1( $865(,&+(1' :(,7 ,1 '(1 g/(.752/8M(5(1 ',586(1 f233(/6&+,&+7P f,( 0(66%$5( i(6$07.$3$=,7>7 e (,1(5 g/(.7O 52'( 6(7=7 6,&+ '(01$&+ $86 '(1 %(,'(1 c17(,/(1 ej '(5 67$55(1 81' e' '(5 ',586(1 f233(/6&+,&+7 =86$00(1P f85&+ ',( u(5,(16&+$/781* '(5 %(,'(1 v(,/.$3$=,7>7(1 *,/7 1$&+ i/P JXPXXK ',( c'',7,21 '(5 5(=,352.(1 y(57(P d(, +2+(1 g/(.752/+(581* .$11 0$1 '$+(5 ef W ej 6(7=(1P h$//6 '$6 1,&+7 *,/7N .$11 0$1 e' %(5(&+1(1 81' '$11 $/6 m255(.785 =85 d(5(&+181* 921 ej 9(5O :(1'(1P k16%(621'(5( @%(5/$*(57 6,&+ '(5 m$3$=,7>76.859( '(87/,&+ '(5 g,19866 '(5
50
a = 0.916 M b = 0.660 M c = 0.100 M NaF d = 0.010 M e = 0.001 M
C D /µF . cm-2
40 b
30
c
20
d e
10 0
a
0.5
0 E pzc -0,5 -1.0 E /V(SHE)
-1.5
c%%P XPSW f,5(5(17,(//( m$3$=,7>7 ef (,1(5 s8(&.6,/%(5(/(.752'( $/6 h81.7,21 '(6 g/(.752O '(1327(17,$/6 g ,1 c%+>1*,*.(,7 921 '(5 m21=(175$7,21 921 p$h J.(,1( 63(=,76&+( c'6253O 7,21 '(6 c1,216 h2KN r27(17,$/ '(5 /$'81*6)5(,(1 g/(.752'( g3=& %(,0 o,1,080 921 ef JgK LTUbP
XPV f,( f233(/6&+,&+7 $1 '(5 r+$6(1*5(1=( g/(.752'(Bg/(.752/7 '(5 ',586(1 f233(/6&+,&+7 e' */(,&+ p8//P f,( 67$55( f233(/6&+,&+7 67(8(57 ,1 p>+(581* :,( (,1 r/$77(1.21'(16$725 (,1(1 327(17,$/81$%+>1*,*(1 d(,75$* =85 i(6$07.$3$=,7>7 %(,P o,7 67(,*(1'(5 k21(167>5.( :,5' '(5 g,19866 '(5 ',586(1 f233(/6&+,&+7 81' '$0,7 e' =85@&.*('5>1*7N :,( 0$1 $86 '(0 x(56&+:,1'(1 '(6 o,1,0806 '(5 m85O 9(1 ,1 c%%P XPSW (171,007P f85&+ o(6681*(1 $1 9,(/(1 u7 ,1 v(,/.$3$=,7>7(1 '85&+)@+5(1 .?11(1\ S S S 3 1 P ej e' ef
JXPXXK
j,6725,6&+ *(6(+(1 :85'(1 ',( (567(1 '(7$,//,(57(1 k1)250$7,21(1 @%(5 ',( f233(/O 6&+,&+7 $1 s8(&.6,/%(5(/(.752'(1 *(:211(1P h@5 ',(6(6 9@66,*( o(7$// .$11 (,1( 6$8%(5( q%(59>&+( 5(&+7 (,1)$&+ '85&+ c8675(7(1 (,1(6 1(8(1 v523)(16 $86 (,1(5 m$3,//$5(1 (5=(8*7 :(5'(1P f(6+$/% :,5' ',(6(6 o(7$// $8&+ )@5 32/$52*5$3+,6&+( x(5)$+5(1 ,1 '(5 (/(.752&+(0,6&+(1 c1$/&+(1 :,( %(, h(67.?53(51 .(,1( t2//(P x21 %(621'(5(0 x257(,/ ,67 ',( o?*/,&+.(,7N ',( i5(1=9>&+(163$1181* 2'(5 i5(1=9>&+(1(1(5*,( $ =8 %(67,00(1P g,1( '(7$,//,(57( f,6.866,21 '(5 v+(502'&+(13+$6( 9(5.1@3)7P C- ,67 ',( c%:(,&+81* '(5 o2/=$+/ (,1(5 u3(=,(6 1- *(*(1@%(5 '(5 */(,&+0>M,*(1
c
n j-n j = Γj A cj
nj A x
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400
-5 γ /10 N
KF 350
NaCl NaBr
300
250
Kl
0.5
0
-0.5 -1.0 E /V(SHE)
-1.5
c%%P XPSY q%(59>&+(163$1181* 921 s8(&.6,/%(5 $/6 h81.7,21 '(6 g/(.752'(1327(17,$/6 Jg/(.752.$3,//$5.859(K )@5 9(56&+,('(1( j$/2*(1,'( J& 3 RPS oK ,0 g/(.752/&+( %(*@167,*(1P f,(6(5 g5(.7 (17)>//7 %(, g3=& 81' )@+57 =8 (,1(0 o$;,080 '(5 q%(59>&+(163$1181* ,1 '(5 g/(.7O 52.$3,//$5.859( %(, )(+/(1'(5 c89$'81*P f,( =:(,7( c%/(,781* '(5 i5(1=9>&+(163$1181* 1$&+ '(0 g/(.752'(1327(17,$/ (5*,%7 ',( ',5(5(17,(//( m$3$=,7>7 ef P u,( 62//7( 1$&+ ef 3
'T $ 'so 32 'g 'g T
JXPYRK
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WXT
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,( STMSpitze
E I II
d
Substrat (Metall, Halbleiter)
III ∆E
(a)
(b)
V0 x
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Pot
E (Spitze = ME 2) Eingang E (Probe = ME 1)
∆E (Bias) Pot
Spitze (ME 2) GE
Diff
RE Probe (ME 1)
Diff
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X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
',( ',( f,&.( '(5 f,586,2166&+,&+7 'p %(6&+5(,%7 LYWbP o,7 ,+5 (5*,%7 6,&+ )@5 ',( ',586,216.21752//,(57( i5(1=67520',&+7( -fN0$; 3 1hf
S T S &E 3 RPXT 1hf U -2 X 6 T &E P 'p
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XPWPX r27(17,$/$%)$// ,0 g/(.752/&+(1+$)7(1 g/(.752'( ,1 (,1(0 g/(.752/&+(\ t/ 3
; ] *
(w/ 3
;P *
JXPSTRK
h@5 (,1( .8*(/O 2'(5 +$/%.8*(/)?50,*( g/(.752'( 0,7 '(0 t$',86 5g *,/7 )@5 =8O 1(+0(1'( g17)(5181* 5 1$&+ (,1)$&+(5 *(20(75,6&+(5 %(5/(*81* t/ 3
5 6 5g ] *J515gK
(w/ 3
5 6 5g P *J515gK
JXPSTSK
f(5 *5?M7( r27(17,$/$%)$// (5)2/*7 +,(5 >+1/,&+ :,( %(,0 m21=(175$7,216*()>//( %(, ',586,216.21752//,(57(1 r52=(66(1 ,1 '(5 p>+( '(5 g/(.752'(12%(59>&+( J6,(+(
Elektrode
Elektrolyt
x
c%%P XPVY n,1($5(5 u7520O 81' f,586,2169(5/$8) J'85&+*(=2*(1( r)(,/(K %=:P m21=(175$O 7,216O 81' u3$1181*63527/ J*(675,&+(/7( n,1,(1K 6(1.5(&+7 =8 (,1(5 9>&+(1+$)7(1 g/(.752'(P
Elektrolyt
passiv Metall
passiv 2 rE
c%%P XPVZ t$',$/6&+( 920 t$',86 5g Jn2&+)5$M $8) 3$66,9(1 o(7$//(1KP
W[Z
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
c%%P XPVXKP m203/,=,(57(5 :(5'(1 ',( x(5+>/71,66( %(, .21.$9 *(.5@007(1 j$/%O .8*(/1 Jc%%P XPVZKP j,(5 *,%7 (6 .(,1( (,1)$&+( $1$/667 6,&+ =(,*(1N '$66 '(5 r27(17,$/$%)$// ,1 81' 80 (,1 +$/%.8*(/)?50,*(6 n2&+ %,6 =80 n2&+%2'(1 &$P '5(,0$/ 62 *52M ,67 :,( %(, (,1(5 .219(; *(.5@007(1 g/(.752'(1O 9>&+( LYYN YZbP f,(6( %(5/(*81*(1 63,(/(1 %(, ,17(16,9(5 /2.$/(5 o(7$//$89?681* :,( %(, '(5 n2&+.25526,21 (,1( t2//( J6P $P c%6&+1P XPXPUN c%%P XPXUKP
XPWPY v5(1181* '(5 %(563$1181*(1 f,( 9(56&+,('(1(1 %(563$1181*(1 $'',(5(1 6,&+ (17635(&+(1' i/P JXPYWK =85 i(O 6$07@%(563$1181*P g,1( c8)75(1181* *(/,1*7 (;3(5,0(17(// '85&+ g,1O %=:P w0O 6&+$/70(6681*(1N '$ 6,&+ '$6 g/(.752'(1327(17,$/ 81' ',( m21=(175$7,2163527/( 925 '(5 g/(.752'( (567 ,1 '(5 =(,7/,&+(1 c%)2/*( (,167(//(1 0@66(1P |85 c1$///( )@5 .85=( %=:P /$1*( |(,7(1 LZSbP
XPWPZ g/(.7521(175$16)(5 $1 j$/%/(,7(5(/(.752'(1 f,( x(5+>/71,66( $1 j$/%/(,7(5(/(.752'(1 6,1' '(87/,&+ 921 '(1(1 $1 o(7$//(1 9(5O 6&+,('(1P c8&+ %(, $865(,&+(1'(5 f27,(581* 921 %,6 =8 SRS[ h5(0'$720(1 352 &0U ,67 ',( |$+/ %(:(*/,&+(5 n$'81*675>*(5 ,0 j$/%/(,7(5 '(87/,&+ ./(,1(5 $/6 ,0 g/(.7O
XPW g/(.752'(1.,1(7,.
-
EF
Eg
Eg
-
- - - - -
EF +
(a)
LB
E-E FB
+ +
+
VB
+
(b)
E = E FB
LB - -
+ +
+
VB
E > E FB
-
Eg
LB - - -
W[[
EF
+ VB
(c)
E < E FB
c%%P XPV[ 1Oj$/%/(,7(5 0,7 x$/(1=%$1' xdN n(,781*6%$1' ndN d$1'$%67$1' g* 81' h(50,O p,9($8 gh )@5 J$K g # gh% N J%K g 3 gh% Jh/$&+%$1')$//K 81' J&K g " gh% P
52/*(5',&+7( ,1 (,1(0 o(7$// %(75>*7 &$P SRTU &02U 81' ,67 '$0,7 '(87/,&+ *5?M(5 $/6 ',( ,0 g/(.752/1'(581*(1 :(5'(1 $/62 9251(+0/,&+ ,1 '(5 t$80/$'81*65$1'6&+,&+7 '(6 j$/%/(,7(56 /2.$/,6,(57 0,7 (,1(5 '$5$86 )2/*(1'(1 32O 7(17,$/$%+>1*,*(1 d$1'9(5%,(*81*P c%%P XPV[ 67(//7 ',( x(5+>/71,66( 0,7 '(0 n(,O 781*6O 81' x$/(1=%$1' 0,7 d$1'$%67$1' g* 81' '(5 f21$725.21=(175$7,21 1f )@5 (,1(1 1Oj$/%/(,7(5 '$5P f,( t$80/$'81*65$1'6&+,&+7 'j/ (5675(&.7 6,&+ 921 '(5 q%(5O 9>&+( ,1 '$6 k11(5( '(6 j$/%/(,7(56P j,(5 ,67 :,('(5 ',( f(%1*( (176&+(,'(1'N ',( 0,7 =81(+0(1'(5 m21=(175$7,21 '(5 n$'81*675>*(5 81' '$0,7 0,7 =81(+0(1'(5 f21$725.21=(175$7,21 $%1,007P k1 i/P JXPVR%K 0866 /(',*/,&+ '(5 )@5 '(1 g/(.752O /5.( k '85&+ 1f (56(7=7 :(5'(1\ #3
|&(& 1.v P R T R f
JXPSTTK
f,( c%+>1*,*.(,7 921 'j/ 920 g/(.752'(1327(17,$/ g ,67 '85&+ i/P JXPSTUK *(*(%(1\ 'j/ 3 #
|T ( Jg2g .v R
K
h%
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o,7 326,7,9(5 :(5'(1'(0 g/(.752'(1327(17,$/ 6(1.7 6,&+ ',( g1(5*,( '(5 g/(.7521(1 ,0 ,11(5(1 j$/%/(,7(5 *(*(1@%(5 '(5 i5(1=9>&+( =80 g/(.752/1'(5 )@+57 J9*/P c%%P XPV[$KP f,( f21$725(1 +$%(1 ,+5 g/(.7521 :(,7*(+(1' $%*(*(%(1 81' ',( o$-25,7>7675>*(5 '(6 1Oj$/%/(,7(56N 'P +P ',( g/(.7521(1 ,1 '(5 t$80/$'81*65$1'6&+,&+7N 9,(M(1 '(0 r27(17,$/*()>//( )2/*(1'
XRR
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
,1 '$6 k11(5( '(6 j$/%/(,7(56 $%P o$1 635,&+7 +,(5 921 (,1(5 x(5$5081*65$1'6&+,&+7P f,( o,125,7>7675>*(5N 'P +P ',( 326,7,9(1 n?&+(5N 5(,&+(51 6,&+ $1 '(5 j$/%/(,7(52%(5O 9>&+( ,0 x$/(1=%$1' $1P f,( c%:(,&+81* '(6 g/(.752'(1327(17,$/6 920 h/$&+%$1'O 327(17,$/ g2gh% ,67 ',( d$1'9(5%,(*81*P d(, g 3 gh% 9(56&+:,1'(7 ',( d$1'9(5O %,(*81*N ',( d>1'(5 9(5/$8)(1 )@5 ',(6(1 h$// +25,=217$/ %,6 =85 q%(59>&+( '(6 j$/%/(,7(56 Jc%%P XPV[%KP d(, (,1(0 $1*(/(*7(1 r27(17,$/ g " gh% /,(*7 (,1( c%:?/O %81* '(5 d>1'(5 925 Jc%%P XPV[&KN 81' ',( g/(.7521(1 '(6 n(,781*6%$1'(6 :(5'(1 $1 '(5 q%(59>&+( $1*(5(,&+(57P o$1 (5+>/7 '(01$&+ )@5 ',(6( u,78$7,21 (,1( c1O 5(,&+(581*65$1'6&+,&+7P d(, (,1(0 3Oj$/%/(,7(5 /,(*(1 ',( c.=(37251,9($86 81' '$6 h(50,Op,9($8 ,1 '(5 p>+( '(5 x$/(1=%$1'.$17( 81' 0$1 +$7 ',( 80*(.(+57(1 x(5O +>/71,66(N 'P +P )@5 g " gh% (,1( c%5(,&+(581* '(5 f()(.7(/(.7521(1 ,0 x$/(1=%$1' Jo$-25,7>7675>*(5K 81' (,1 c15(,&+(581* '(5 g/(.7521(1 $1 '(5 q%(59>&+( Jo,12O 5,7>7675>*(5KP h@5 g # gh% 5(,&+(51 6,&+ 80*(.(+57 ',( 326,7,9(1 n?&+(5 $1 '(5 q%(5O 9>&+( $1P f,( m$3$=,7>7 (,1(6 j$/%/(,7(56 ,1 m217$.7 0,7 (,1(0 g/(.752/7(1 $8)*()$667 :(5'(1P d(, $865(,&+(1' +2+(5 k2O 1(167>5.( ,0 g/(.752/66,*7 :(5'(1 81' ',( i(6$07.$3$=,7>7 (5*,%7 6,&+ $86 '(5 c'',7,21 '(5 5(=,352.(1 m$3$=,7>7(1 '(5 67$55(1 j(/0+2/7=Ou&+,&+7 ej 81' '(5 t$80/$'81*65$1'6&+,&+7 ej/ '(6 j$/%O /(,7(56\ S S S S 3 1 W P JXPSTVK ej ej/ ej/ e ej %(75>*7 ,P cP SR %,6 TR =h &02TP ej/ ,67 '(87/,&+ ./(,1(5N :$6 (,1(5 *5?M(5(1 5>80O /,&+(1 c86'(+181* '(5 t$80/$'81*65$1'6&+,&+7 ,1 '(1 j$/%/(,7(5 +,1(,1 (17635,&+7N 62 '$66 SBe $11>+(51' */(,&+ SBej/ :,5'P f,( f21$725(1.21=(175$7,21 />667 6,&+ $86 '(5 r27(17,$/$%+>1*,*.(,7 '(5 m$3$=,7>7 '(6 j$/%/(,7(56 0,77(/6 '(5 u&+277.*7 0$1 SBe T *(*(1 g $8)N (5*,%7 6,&+ '(5 u&+1,77381.7 0,7 '(5 c%6=,66( %(, g 3 gh% P c86 '(0 c167,(* )2/*7 ',( m21=(175$7,21 '(5 n$'81*675>*(5 1P u,( (17635,&+7 %(, (,1(0 1Oj$/%/(,7(5 $11>+(51' '(5 f21$725.21=(175$7,21 1f %=:P %(, (,1(0 3Oj$/%/(,7(5 '(5 c.=(3725.21=(175$7,21P c%%P XPWR =(,*7 (,1 d(,63,(/ )@5 |,11O ',2;,'6&+,&+7(1 817(56&+,('/,&+(5 f27,(581*N ',( '85&+ 3*7(1 g/(.752'(1327(17,$/6 g 920 h/$&+%$1'327(17,$/ gh% P j,(5)@5 :85'( '(5 g;321(17,$/$86'58&. ,1 (,1(5 v$&+( -r+Nf,))\ lr+N*(6 3 -r+ 1-r+Nf,)) 3 ( IR
S2(2" 'I( P S1" nr
JXPSTZK
f,(6(5 c17(,/ .$11 9(51$&+/>66,*7 :(5'(1N :(11 ',( 237,6&+( n>1*( SB" *52M *(*(1 ',( f,586,216/>1*( '(5 o,125,7>76/$'81*675>*(5 nr ,67 J" nr * SKN 81' i/P JXPSTZK *(+7 ,1 i/P JXPSTXK %=:P JXPSTYK @%(5P g,1( :(,7(5( :,&+7,*( d(=,(+81* )2/*7N :(11 ,1 i/P JXPSTXK ',( c%+>1*,*.(,7 '(6 c%62537,216.2(5,=,(17(1 " 921 '(5 c15(*81*6(1(5*,( + - ,1 '(5 p>+( '(6 y(57(6 '(6 d$1'$%67$1'(6 g* '85&+ 1
" 3 &2167P
J+ -2g*KT +-
JXPST[K
(,1*()@+57 :(5'(1 .$11P f,( 5(68/7,(5(1'( i/(,&+81* 1 + - -r+ 3 (()) + - 3 &2167P |g2gh% 'j/ J+ -2g*KT (R IR
JXPSURK
(50?*/,&+7 (6N '85&+ (,1( c8)75$*81* '(5 g5,=,(1= (()) '(6 r+272675206 *(*(1 ',( c15(*81*6(1(5*,( + - '(1 d$1'$%67$1' g* '85&+ g;75$32/$7,21 =8 %(67,00(1P f(5 g;321(17 1 %(5@&.6,&+7,*7N 2% (6 6,&+ %(, '(5 r+272$15(*81* '(5 g/(.7521(1 80 (,1(1 ',5(.7(1 2'(5 (,1(1 ,1',5(.7(1 %(5*$1*N 'P +P (,1(1 237,6&+(1 %(5*$1* 0,7 g5+$/7 2'(5 }1'(581* '(6 k038/6(6 '(5 g/(.7521(1N +$1'(/7P j>87* =(,*(1 ',( ,1O ',5(.7(1 %(5*>1*( (,1(1 ./(,1(5(1 d$1'$%67$1'N '$ '(5 g1(5*,(817(56&+,(' '(5 %(7(,/,*7(1 %(6(7=7(1 |867>1'( ,0 x$/(1=%$1' 81' '(5 81%(6(7=7(1 ,0 n(,781*6%$1'
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
(η eff hν )2
1.0
Cu 0.1 M KOH AsO43-/AsO33 E =-0.13 V
AsO43-/AsO33
0.5
0 (a)
1.0
(η eff hν )1/2
XRX
2
3 h ν /eV
4
0.5 [Co(NH3)5Cl]2+
0 (b)
2
3 h ν /eV
4
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XPX g,1,*( c1:(1'81*(1 (/(.752&+(0,6&+(5 o(7+2'(1 81' m21=(37(
XRY
&+(581* @%(5 c1$/&+( j$/%/(,7(5Bg/(.752/7(1 $86*(/?67N u2/$5=(//(1 0,7 '(0 |,(/ $8)=8%$8(1N ',( g1(5*,( '(6 n,&+7(6 $/6 (/(.75,6&+( g1(5*,( ',5(.7 =8 187=(1 2'(5 ,1 h250 $1'(5(5 g1(5*,(75>*(5 =8 63(,O &+(51N :,( =P dP $/6 (/(.752&+(0,6&+ (5=(8*7(5 y$66(56725P j,(51$&+ *,%7 (6 =:(, m21=(37(N ',( ,1 c%%P XPWX$ 81' % 6.,==,(57 6,1'P f85&+ n,&+7$%62537,21 :(5'(1 n$'81*675>*(53$$5( ,0 j$/%/(,7(5 (5=(8*7N ',( ,1 '(66(1 t$80/$'81*65$1'6&+,&+7 *(75(117 :(5'(1P d(, '(0 ',5(.7(1 x(5%5$8&+ (/(.75,6&+(5 g1(5*,( :(5'(1 ',( f(O )(.7(/(.7521(1 $1 '(5 j$/%/(,7(52%(59>&+( $..808/,(57 81' 5($*,(5(1 0,7 (,1(0
-
hν
-
E VB (a)
E LB -
+
EF
Metall
hν
-
+
-
-
Ox+
Redox-Elektrolyt
1 2 H2
n-Halbleiter
-
Red
n-Halbleiter
E VB (b)
Red
+
+
Energie
EF
Ox+
Wel
E LB -
-
+ OH 1 2 H2O
Elektrolyt
H2O 1 4 O2
-
-
-
Wchem
EF
+ H+ Metall
c%%P XPWX J$K g/(.752&+(0,6&+( 5(*(1(5$7,9( u2/$5=(//( 0,7 (,1(0 1Oj$/%/(,7(5 =85 ',5(.7(1 g5=(8*81* 921 (/(.75,6&+(5 c5%(,7 y(/ P J%K g/(.752&+(0,6&+( u2/$5=(//( 0,7 (,1(0 1Oj$/%/(,7(5 =85 g5=(8*81* 921 jT $/6 g1(5*,(75>*(5 '85&+ y$66(5=(56(7=81*P e+(0,6&+( c5%(,7 y&+(0 :,5' (5=(8*7P
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(a)
5µ
(b)
XSW
30 µ
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XSX
0 (a)
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
5
10
15
20
25 nm
(b) 10 µm
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180 nm 2 nm 0 0 180 nm
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XS[
STM-Spitze
Mz+
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JXPSU[K
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XUX
X g/(.752'(1N g/(.752'(1352=(66( 81' g/(.752&+(0,(
UME
1.0
negative Rückkopplung
0.8
IT I T, ∞
0.6 0.4 0.2 0 (a)
0
1.0
(b)
Isolator
2.0 d r
3.0
4.0
5.0
c%%P XPYW J$K w/75$0,.52(/(.752'( (,1(6 ugeo ,1 m20%,1$7,21 0,7 (,1(0 k62/$725P J%K '$6 *(0(66(1( u752067>5.(19(5+>/71,6 kv BkvNZ ,1 c%+>1*,*.(,7 920 c%67$1' ' %(, 1(*$7,9(5 t@&.O .233/81*P JugeoN (/(.752&+(0,6&+(6 t$67(50,.526.23PK
positive Rückkopplung
UME
8
IT
I T, ∞
6
2
Ox
Red
4
0 (a)
Leiter
(b)
0
1
2 d r
3
4
5
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rm \ rp$ \ re/ 3 S \ RPRV \ RPVW N
JXPSVSK
c.7,216=867$1'\ rm \ rp$ \ re/ 3 S \ TR \ RPVW P f,( m21=(175$7,2169(5+>/71,66( '(5 k11(1O 81' c8M(1/?681* 6,1' ,1 v$%P XPZ Jp(5O 9(1=(//(K $8)*()@+57P q5(1%$5 ,67 ',( p(59(10(0%5$1 )@5 $//( :(6(17/,&+(1 m$7,21(1
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h526&+086.(/ (35 32RPR[R x
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c8M(1/?681*
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RPRWR o p$1 RPVRR o m1 RPRVRARPSRR o e/2
RPVXR o p$1 RPRSR o m1 RPWVR o e/2
RPRR[ o p$1 RPSVR o m1 RPRRUARPRRV o e/2
RPSTR o p$1 RPRRT o m1 RPSTR o e/2
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XZW
Transmission
E /kVcm-1
n
µ
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antiferro
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YPV f,( 60(.7,6&+(1 r+$6(1
XZY
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E Eth
E =0
ferroelektrisch synklin
antiferroelektrisch antiklin
razemisch
E Eth
ferroelektrisch antiklin
E =0
antiferroelektrisch synklin
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+
NaN
8
58
40
(a) 14 12 10 8
55 13
19
23 26 29 32 34
43 46 49
61 64
71 74
6 4
87
+
AnN
2 0 10 (b)
81
20
30
40
50 Clustergröße N
60
70
80
90
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SN SN SN SN SN SN SN SN SN
heiß
kalt
4 5 (a)
6
7
8 9 10 11 12 13 14 15 16 Masse/Na
SUN WWN SVY YN TUN WVN SRW SUN WWN SVY YWN SVY XN S[N VVN ZWN SVX SUN WWN SVY UZN SSX VN SRN TRN UWN WXN ZVN STR SWN XW
4 5 (b)
6
7
8 9 10 11 12 13 14 15 16 Masse/Na
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(Ca)n n=171
300 100
n=1412 922 561
50
(Nal)nNa+
364
2053 2865
665 1098
62
3865 5075
0
200 100
-50 0
3000 4000 1000 2000 Anzahl der Atome/Cluster
5000
0
100000 Anzahl der Atome/Cluster
200000
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(e)
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Datenerfassung und Steuerung
Nd: YAG Laser 2
Gittermotor
Helium (2 bar)
Gittermotor
Nd: YAG Laser 1
Probe
HV-Schalter
SHG Skimmer
HV - Spannungsversorgung
SHG
Oszilloskop
Signal
MCP
Turbopumpe 1
Repeller
Strahl + Laser
Deflektor
Turbopumpe 2
Driftkammer
Nachbeschleunigung
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-HV -HV lin. Spannungsrampe/+HV +/-HV Puls
Signal
Öl-Diffusionspumpe
Düse
2 3 Uhr 4 5 6 1
Farbstofflaser 1
Farbstofflaser 2
Nd
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Güteschalterpuls
ZVZ [ e/867(5
[PV u3(.7526.23,6&+( o(7+2'(1
ZV[
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ZWR
[ e/867(5
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532 nm
Gitter
TS Verstärker
1064 nm
Farbstofflaser
LiNbO3 Stellmotor
Filter Filter 1064 Dye IR-Laser
λ /2-Platte (optional)
Differenzfrequenzmischung
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Oszillator Vorverstärker
Nd: YAG-Laser
[PV u3(.7526.23,6&+( o(7+2'(1 ZWS
ZWT
[ e/867(5
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Ionisationspotential/eV
[PW c//( g,*(16&+$)7(1 >1'(51 6,&+ 0,7 '(5 e/867(5*5?M( 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
W∞+
(Z+α ) e
IP
rs N 1/3+ δ
Nbn
200
W∞ = 4.3 eV rs = 0.163 nm δ α 0
= 0.1 nm = 0.18 0.1
0.2
ZXW
4
EA
0.3 N -1/3
12 0.4
0.5
0.6
0.7
c%%P [PUT i(0(66(1( g/(.7521(1$5,1,7>7(1 81' k21,6,(581*6(1(5*,(1 921 p,2%&/867(51P f,( k21,6,(581*6(1(5*,( =(,*7 (,1( 9,(/ 6&+:>&+(5( pOc%+>1*,*.(,7 $/6 %(,0 p$75,80P
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B
Clusterstrahl
m d
z vx
x y
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[PW c//( g,*(16&+$)7(1 >1'(51 6,&+ 0,7 '(5 e/867(5*5?M(
ZXY
6(/:,5.81* =:,6&+(1 '(1 f20>1(1 0?*/,&+67 *(5,1* :,5'P p81 ,67 '(5 f85&+0(66(5 (,1(5 f20>1( JSRR2SRRR 10K ,00(5 6(+5 *52M *(*(1@%(5 '(0 (,1(6 e/867(56P f$6 %('(87(7N '$66 ,0 e/867(5 $//( f5(+,038/6( *(.233(/7 6,1' 81' (,1(1 5,(6,*(1 i(O 6$07'5(+,038/6 %,/'(1P y(11 =P dP %(, (,1(0 e/867(5 921 SRRR c720(1 -('(6 c720 (,1(1 u3,1 921 S @ %(,75>*7N 62 (5*,%7 6,&+ (,1 = 921 SRRR @P g5+,7=7 0$1 (,1 0$.526.23,6&+(6 u7@&. g,6(1N 62 :,5' 6(,1 o$*1(7)(/' ,00(5 ./(,1(5N 80 $0 e85,(Or81.7 =8 9(56&+:,1'(1P o$.526.23,6&+(6 h( ,67 $/62 (17:('(5 )(552O 2'(5 3$5$0$*1(7,6&+P h@5 ./(,1( v(,/&+(1 *,%7 (6 '$=:,6&+(1 12&+ '(1 u8O 3(53$5$0$*1(7,6086P o$1 .$11 ,0 e/867(5 $/62 '5(, d(5(,&+( 817(56&+(,'(1N ,1 '(1(1 6,&+ ',( 0$*1(7,6&+(1 g,*(16&+$)7(1 48$/,7$7,9 817(56&+(,'(1\ )(5520$*1(7,6&+\ d(, 7,()(1 v(03(5$785(1 6,1' $//( (/(.7521,6&+(1 u3,16 *(.233(/7 81' '(5 i(6$07'5(+,038/6 +$7 (,1( )(67( 5>80/,&+( t,&+781* ,0 e/867(5P o$1 %5$8&+7 ',( 62 *(1$117( 0$*1(7,6&+( m5,67$//(1(5*,( 2'(5 c1,627523,((1(5*,(N 80 ,+1 $86 ',(6(5 t,&+781* /(,&+7(5 o$*1(7,6,(581* +(5$86=8'5(+(1P 683(53$5$0$*1(7,6&+\ y,5' ',( 7+(50,6&+( g1(5*,( *5?M(5 $/6 ',( c1,627523,((1(5O *,(N $%(5 12&+ 1,&+7 *52M *(18*N 80 '(1 6(+5 *52M(1 i(6$07'5(+,038/6 = ,1 6(,1( $720$5(1 m20321(17(1 $8)=8%5(&+(1N 62 :,5' = )5(, ,0 t$80 98.78,(5(1P f85&+ (,1 o$*1(7)(/' .$11 = ,0 t$80 )(67*(+$/7(1 :(5'(1N :$6 817(1 *(1$8(5 ',6.87,(57 :,5'P u,1.7 ',( v(03(5$785 817(5 ',( 62 *(1$117( d/2&.,1*Ov(03(5$785N 5$67(7 = *(*(1@%(5 '(0 i,77(5 (,1 81' 0$1 %(.2007 )(5520$*1(7,6&+(6 x(5+$/7(1P u7(,*7 ',( v(03(5$785 @%(5 ',( e85,(Ov(03(5$785N :,5' '(5 e/867(5 3$5$0$*1(O 7,6&+P 3$5$0$*1(7,6&+\ f,( 7+(50,6&+( g1(5*,( ,67 *5?M(5 $/6 ',( u3,1Ou3,1Om233/81*6O (1(5*,(N 81' ',( u3,16 6,1' '$0,7 81*(.233(/7P o$1 %(.2007 (,1 x(5+$/7(1 :,( 921 p 81*(.233(/7(1 u3,16P k1 c%%,/'81* [PUV 81' [PUW 6,(+7 0$1N :,( '$6 *(0(66(1( 0$*1(7,6&+( o20(17 921 '(5 e/867(5*5?M( $%+>1*7 LYYN YZbP f$6 *52M( c1)$1*6:(57 ./(,1(5 e/867(5 )>//7 =,(0/,&+ 6&+1(// =80 h(67.?53(5:(57 $%P f,( f$7(1 =(,*(1 5(352'8=,(5%$5( x$5,$O 7,21(1N ',( ,1 c%%P [PUW )@5 p, %(66(5 $8)*(/?67 6,1'P f,( o,1,0$ 75(7(1 (17:('(5 %(, k.26$('(5$%6&+/@66(1 Jp 3 SUK 2'(5 *$1= ,1 '(5 p>+( '$921 $8)P d(, ',(6(1 6(+5 .203$.7(1N 61*,*.(,7 71'(7 6,&+ ,1 LYWN YXN Y[bP h@5 ',( c1:(1'81*(1 6,1' 1,&+7 185 ',( 0$*1(7,6&+(1 o20(17(N 621'(51 $8&+ ',( d/2&.,1*Ov(03(5$785 :,&+7,*N ',( (%(1)$//6 921 '(5 i5?M( '(6 e/867(56 $%+>1*7P d(, '(1 7+(25(7,6&+(1 d(5(&+181*(1 :85'( =8 c1)$1* 185 '(5 u3,1 %(5@&.6,&+7,*7N 81' ',( g5*(%1,66( )@5 ',( 0$*1(7,6&+(1 o20(17( :$5(1 ,00(5 ./(,1(5 $/6 ',( (;3(5,0(17(//(1P f$6 r52%/(0 ./>57( 6,&+ $8)N $/6 .@5=/,&+ 62:2+/ 7+(25(7,6&+ LY[b $/6 $8&+ (;3(5,0(17(// LZRb *(=(,*7 :85'(N '$66 )@5 p,&.(/ ',( d(,75>*( '(6 (/(.752O 1,6&+(1 f5(+,038/6(6 1,&+7 =8 9(51$&+/>66,*(1 6,1' 81' )@5 p 6 SR %,6 =8 VR@ '(5 *(6$07(1 o$*1(7,6,(581* $860$&+(1 .?11(1P f$6 =8 c1)$1* @%(55$6&+(1'( (;3(5,0(17(//( g5*(%1,6N '$66 (,1 e/867(5675$+/ ,0 u7(51Oi(5/$&+Oo$*1(7 1,&+7 $8)63$/7(7N 62// 12&+ (,10$/ *(1$8(5 ',6.87,(57 :(5'(1P c0 %(67(1 9(567$1'(1 ,67 '(5 h$// '(6 683(53$5$0$*1(7,6&+(1 e/867(56P y(11 6(,1 i(6$07'5(+,038/6 = .(,1( y(&+6(/:,5.81* 0,7 '(1 t27$7,21(1N x,%5$7,21(1 (7&P '(6 e/867(56 +$7N 62 %/(,%7 = 1$&+ t,&+781* 81' i5?M( (5+$/7(1 81' 63$/7(7 ,0
ZXZ
[ e/867(5 1.2 Ni 1.0
0.8
Festkörper
0.6 (a) magnetisches Moment pro Atom/µB
0.4
(b)
2.6 Co
2.4 2.2 2.0 1.8
Festkörper
1.6 1.4 3.4
Fe
3.0 2.6 Festkörper
2.2 1.8 (c)
0
100
200 300 400 Clustergröße N
500
600
700
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[PW c//( g,*(16&+$)7(1 >1'(51 6,&+ 0,7 '(5 e/867(5*5?M( Ni5
1.8
ZX[
Nickelcluster
magnetisches Moment/µB
Ni8
1.4
Ni71
1.0 Ni13 0
10
Ni34
Ni56
20 30 40 50 60 70 Anzahl der Atome pro Cluster
80
90
100
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300 K
3100 K
(a) 0.06
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PDOS (bel. Einheiten)
ρ0 (r )e (bel. Einheiten) (b)
0.25
300 K
0.05
1000 K
0.03 0.02 3100 K
0.01 0
1
2
5 3 4 6 r (bel. Einheiten)
7
8
9
10
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1000 K
0.15 0.10 0.05 0
(c)
300 K
0.20
0
2
4
6 8 υ (THz)
10
12
14
16
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1350 1300
flüssig
1250
Dh
Temperatur/K
1200
Ih
1150 1100 1050 1000 950 900
5
10 Durchmesser/nm
15
20
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ZYV
[ e/867(5 Flugzeit t /µs 100
200
Intensität (bel. Einheiten)
hγ 100
0
20
30
40 50 Clustergröße
60
70
80
90
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[PW c//( g,*(16&+$)7(1 >1'(51 6,&+ 0,7 '(5 e/867(5*5?M( Tsiede
Tschmelz Esiede 15
ZYW
+ Na139
Energie/eV
10
5
0
0
100 150 200 250 300 350 400 450 500 Temperatur/K
50
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normierte Schmelztemperatur
1.0
bcc
ico
?
0.9 ~104
0.8
55 3
~10 0.7
299 181
142
0.6 0.5
0
0.15 0.20 0.05 0.10 N -1/3~inverser Clusterradius
0.25
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[VV
[ e/867(5
Bestrahlen mit Laserlicht der Wellenlängen λ 1 und λ 2
Absorptionskoeffizient
große Cluster Laserlicht mit λ 1
gewünschte Größe
kleine Cluster Laserlicht mit λ 2
Photonenenergie nach Laserbeschuss
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[PY e/867(5 $8) q%(59>&+(1 vor Laserbestrahlung
[VW
nach Laserbestrahlung
5 nm
5 nm
0
500 nm
0
500 nm
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(a)
allgemeiner Fall
E = E(t)
(b)
quasistatischer Fall
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[VY
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y$&+67806.,1(7,. 81' .$7$/3$5$7,21 '(5 r52%(1N ,16%(621'(5( '$11N :(11 ',( p$127(,/&+(1 85635@1*/,&+ $8) ',(/(/(.75,6&+(1 o$7(5,$/,(1 0,7 7&+(1 ,0 w/75$+2&+9$.880 2'(5 817(5 n$%25%(',1*81*(1 0,7 t$67(5O .5$)7O 2'(5 t$67(57811(/0,.526.23,( $%=8%,/'(1P t$67(57811(/0,.526.23,( .$11 $%(5 1$785*(0>M 185 '$11 (,1*(6(7=7 :(5'(1N :(11 '$6 9(5:(1'(7( u8%675$7 /(,7)>+,* ,67N %(,63,(/6:(,6(N :(11 ',( e/867(5 $8) (,1(5 '@11(1 q;,'6&+,&+7 (,1(5 j$/%/(,7(5O 2'(5 o(7$//2%(59>&+( 35>3$5,(57 :85'(1P j>87* 67(//7 0$1 6,(N 6,(+( 2%(1N $%(5 $8) f,(/(.75,.$ :,( s8$5=N i/,00(5N u$3+,5 2'(5 u$/=.5,67$//(1 +(5P k1 62/&+(1 h>/O /(1 .2007 ',( tmo J6P c%6&+1P XPVPUPUK $/6 %,/'*(%(1'(6 x(5)$+5(1 =80 g,16$7=P f$%(, 6,1' $//(5',1*6 (,1,*( d(621'(5+(,7(1 =8 %($&+7(1P k16%(621'(5( ,67 ,1 9,(/(1 h>//(1 '(5 m5@0081*65$',86 '(5 u21'(163,7=( 9(5*/(,&+%$5 2'(5 62*$5 *5?M(5 $/6 ',( c86'(+181* '(5 p$127(,/&+(1 $8) '(5 u8%675$72%(59>&+(P y,( c%%P [P[R 6&+(O 0$7,6&+ =(,*7N :(5'(1 '$11 ',( /$7(5$/(1 c%0(6681*(1 '(5 e/867(5 =8 *52M :,('(5O *(*(%(1P f(1 d,/'(51 .$11 /(',*/,&+ ',( j?+( '(5 v(,/&+(1 %(=@*/,&+ '(5 u8%675$7O 2%(59>&+( (171200(1 :(5'(1P f(112&+ />667 6,&+ ',( c86'(+181* '(5 e/867(5 ,1
20 nm
c%%P [PZ[ g/(.7521(10,.526.23,($8)1$+0( .5,67$//,1(5 i2/'&/867(5 $8) u$3+,5P f(5 0,77/(5( f85&+0(66(5 ,1 '(5 u8%675$7(%(1( %(75>*7 J[ 8 TK 10P
[WT
[ e/867(5
AFM-Spitze
R ≈ 15 nm
Scanlinie
Substrat mit Nanoteilchen
c%%P [P[R u&+(0$7,6&+( f$567(//81* '(5 c%%,/'81* 921 p$127(,/&+(1 0,7 t$67(5.5$)7O 0,.526.23,(P y(*(1 '(6 (1'/,&+(1 m5@0080*65$',86 '(5 u21'(163,7=( 921 7&+(11250$/(1 .255(.7 5(352'8=,(57P
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Spektrometer
N2 CCD
Strahlteiler
Okular Linse
evaneszentes Feld
Objektiv Probe
Prisma weißes Licht
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nach Bestrahlung
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Γ hom /meV
70
T2 /fs
22 20 18 16 14 12 10 8 6 4 2 0
600 0 5 15 20 10 äq. Radius der resonanten Nanoteilchen/nm
25
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E-Feld
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+
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Zahl der Ereignisse
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