Tables of Molecular Vibrational Frequencies - Consolidated Volume I

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Contents Page

Foreword. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

III

1. Introduction..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Molecules selected and their ordering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Description of Tables. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Symmetry.................................................. 3.2 Symmetry number. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Symmetry species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Numbering of frequencies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5 Approximate type of mode..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6 Selected value of frequency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7 Infrared and Raman spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.8 Comments.................................................. 3.9 References................................................. 4. Tables of vibrational frequencies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Empirical formula index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

1 1 2 2 2 2 2 2 2 3 3 3 3 158

IV

TABLE

I.

Ordering of symmetry species

(In the present volume small letters are used to designate the species of fundamental frequencies) Symmetry species

Point group

TABLE

II.

Point group

Definition of local symmetry coordinates

(c) Local symmetry coordinates for the CR group (see fig. Ic) CR stretching: ~rCH CR bending: (2~(3HX - ~(3HY - ~(3Hz)1 v!6 (~(3HY - ~(3HZ) 1v!2 (d) Local symmetry coordinates for the planar CR 2 group (see fig. Id) CR 2 symmetrical stretching: (~rl ~r2) 1 v!2 CR 2 antisymmetrical stretching: (~rl - ~r2) 1 v!2 CR 2 scissors: (2~a - ~(31 - ~(32) 1v!6 CR 2 rocking: (~(31 - 6.(32) 1v!2 CR 2 wagging: ~o -sin a. (e) Local symmetry coordinates for the planar CR group (see fig. Le) CR stretching: tlrCH in-plane CR bending: (~(3HX - ~(3HY) 1v!2 out-of-plane CR bending: ~OH ·sin'YXY.

(a) Local symmetry coordinates for the CR a group (see fig. La) CR a symmetrical stretching: (~rl ~r2 ~ra) 1 v!3 CR a degenerate stretching: (2~rl - ~r2 - ~ra)1 v!6 (~r2 - ~ra)1 v!2 CR a symmetrical deformation: (~a2a ~a31 ~a12 - ~(31 - ~(32 - ~(3a) 1v!6 CR a degenerate deformation: (2~a23 - ~aal - ~(12) 1v!6 (~a31 - ~(12) 1v!2 CR a rocking: (2~(31 - ~(32 - ~(3a) 1v!6 (~(32 - ~(3a) 1v!2. (b) Local symmetry coordinates for the CR 2 group (see fig. Ib) CR 2 symmetrical stretching: (~rl ~r2) 1 v!2 antisymmetrical stretching: (~rl - ~r2) 1 v!2 CR 2 scissors: (4~a - ~(31X - ~(32X - 6.(31Y - ~(32Y) 1v!20 CR 2 wagging: (6.(31X ~(32X - ~(31Y - ~(32y)/2 CR 2 twisting: (~(31X - ~(32X - ~(31Y ~(32Y) 12 CR 2 rocking: (~(31X - ~(32X ~(31Y - ~(32Y) 12.

+

+

+

+

+

+

+

+

Symmetry species

+

7

H H H

H

z

x x x (0 )

( b)

(c)

H

H

x

x (d) FIGURE

TABLE

Notation

y

(e)

1. Parameters of methyl, methylene, and methin groups,

III.

Uncertainty code for the selected values offrequencies Basis*

Uncertainty cmr?

A

0'"'-'1

B

1'"'-'3

C

3'"'-'6

(i)

D

6'"'-' 15

(i)

(i) (ii) (i) (ii)

Gas, prism spectrometer, low resolution (e.g., 1000 '"'-' 2000 em"? for NaCI prism). (ii) Solid, liquid or solution, accurate measurement.

(ii)

E

15 '"'-' 30

Gas, grating spectrometer, rotational fine structure accurately analyzed. Gas, grating spectrometer, a sharp Q branch. Gas, grating spectrometer, rotational fine structure partly analyzed. Gas, prism spectrometer, fairly high resolution (e.g., 700 '"'-' 1000 em"? for NaCI prism).

Gas, prism spectrometer, very low resolution (e.g., >2000 em"! for NaCI prism). Solid, liquid or solution, inaccurate measurement.

(i) Value estimated from Fermi resonance doublet. (ii) Value estimated from overtone or combination tone. (iii) Calculated frequency.

* The uncertainty assigned here to each method of measurement is a typical value; greater accuracy is often achieved with some of the methods.

8

Molecule: MolybdenuIll hexafluoride MoF6 SYIllIlletry Oh SYIllIlletry nUIllber d = 24

Sym. species

No.

Selected value of frequency

Approximate type of mode

No. 52

Infrared

Raman

cm- l

cm- l (Gas) 741.5 VS, p 651.~ W, dp la la 318 W,dp

(~as) al o

VI

eo

V2 V3

flu

V4 V5

f 20

Sym. stretch ............ Deg. stretch ............ Deg. stretch ............ Deg. deform ............ Deg. deform ............ Deg. deform ............

1

742 652 741 264 318 116

B B C C C E

la la 741 VS 264 S la la

Comments

References H. H. Claassen, H. Selig, and J. G. MaIm, J. Chern. Phys. 36, 2888 (1962). B. Weinstock and G. L. Goodman, Advan. Chern. Phys. 9, 169 (1966), and references cited there. H. H. Claassen, G. L. Goodman, J. H. Holloway, and H. Selig, J. Chern. Phys. 53, 341 (1970).

[1] IR.R. [2] IR.R.

[3] R.

No. 53

Molecule: Tungsten hexafluoride WF6 SYIllmetry Oh SYIllIlletry nUIllber d

Sym. species

No.

al o

VI

eo

V2

flu

V3 V4

f 20

V5

f2u

V6

Approximate type of mode

Sym. stretch ............ Deg. stretch ............ Deg. stretch ............ Deg. deform ............ Deg. deform ............ Deg. deform ............

24

Selected value of frequency

771 677 712 258 320 127

B B C C C E

I

Infrared

Raman

cm- l (Gas) la la 712 VS 258 S la la

cm- l (Gas) 771.0 VS, p 677.2. W, dp la la 320 W,dp la

Comments

I

OC

(2V6)

I

References [1] IR.R. [2] IR. f3] R.

B. Weinstock and G. L. Goodman, Advan. Chern. Phys. 9, 169 (1966), and references cited there. S. Abramowitz and I. W. Levin, Inorg. Chern. 6, 538 (1967). H. H. Claassen and H. Selig, Israel J. Chern. 7, 499 (1969).

34

[3].

Molecule Diborane-d 6 Symmetry D2h

Sym. species

Approximate type of mode

No.

blg

V6

C C C D

la la la a592 VW

Ring stretch ............ BD2 wag ............... BD2 a-stretch ........... BD2 rock ............... Ring puckering .......... BD2 a-stretch ...........

1273 870 1999 705 262 1980

C E C E C E

la la 1999 VS

BD2 rock ............... Ring stretch ............

740 E 1465 E

BD2 wag ............... BD2 twist .............. ' BD2 s-stretch ...........

728 C 730 C 1845 C

Vs Vg

b 2g

VlO Vn

b 2u

V13

Vl2 V14

Vl6 Vl6

b 3g b 3u

cm- l (Gas) la

1511 929 726 592

V7 b lu

Infrared

Ring stretch ............ BD2 scis. '" ............ Ring deform ............ BD2 twist ..............

V4 V6

Selected value of frequency

1860 E

V2 , V3 au

Ko.57 4

BD2 s-stretch ...........

Vl

a g

lOB 2D 6 Symmetry number d

I

V17

VlS

Ring deform ............ BD2 scis ................

1205 C 881 C

Raman

cm- l (Liquid) f1880 VS, p }FR \1833 S, P 1511 VS, p 929 p 72~ VS, p la

a

1273 (2) dp

la ........... la OC (Vg 262 M la la f 1975 (9) dp \ (2000 (5))dp la ............ OC (VlO la f1491 M FR (vs \1459 MS 728 S la la 73~ (4) dp la f 1857 VS FR (V3 \ (1799 S) 1205 VS la la 881 VS

} }

Observed very weakly and also confirmed by combination bands.

References r1] IR. [2] IR.R. [3] R. [41 Th.

A. R. R. T.

N. Webb, J. T. Neu, and K. S. Pitzer, J. Chern. Phys. 17, 1007 (1949). C. Lord and E. Nielsen, J. Chern. Phys. 19, 1 (1951). C. Taylor and A. R. Emergy, Spectrochim. Acta 10, 419 (1958). Ogawa and T. Miyazawa, Spectrochim. Acta 20, 557 (1964).

38

(2V3)'

............ OC (vs

I

-

Comments

+ +

V7). VlO).

+ V12). + V7).

+ VlS)'

Molecule: Cyanogen chloride 35CICN SYIllIlletry C oov SYIllIlletry nUIllber d S~.

No.

speCIes

(7"+

VI

V2 V3

7r

(7"+

Approximate type of mode

CN stretch ............. Bend .................. CCI stretch .............

No. 64 1

Selected value of frequency

Infrared

cm- I

cm- 1

2216 A 378 A 744 C

(Gas) 2215.6VS 380 S J 782.6 S t 714.0 S

(Liquid) 2206 (10) 394 (3) 730 (5)

Raman

}

Comments

RP [2]. FR (2V2) [2].

References W. O. Freitag and E. R. Nixon, J. Chern. Phys. 24, 109 (1956), and references cited there. W. J. Lafferty, D. R. Lide, and R. A. Toth, J. Chern. Phys. 43, 2063 (1965).

[1] IR.R. [2] IR.

Molecule: Cyanogen chloride 37CICN SYIllIlletry C oov SYlllllletry nUlllber d

Sym. species

No.

(7"+

VI

7r

(7"+

I

V2 V3

A pproxima te type of mode

CN stretch ............. Bend .................. C CI stretch. . . . .........

No. 65 1

Selected value of frequency

2215 A 378 A 736 C

References See No. 64.

42

Infrared

Raman

,

cm- I

cm- 1

I

(Gas) 2215.3VS 380 S

(Liquid) 2206 (10) 394 (3) 730 (5)

I·········· .

Comments

RP [2]. FR (2V2) [2].

Molecule: Formaldehyde H 2CO Symmetry C 2v Symmetry number d

Sym. species

Approximate type of mode

No.

CH 2 s-stretch ........... CO stretch ............. CH 2 scis ................ CH 2 a-stretch ........... CH 2 rock ............... CH 2 wag ...............

VI

al

V2

Va

bl

V4 V5 V6

b2 I

No. 68 2

Selected value of frequency

2783 A 1746 A 1500 A 2843 A 1249 A 1167 A

Infrared

Raman

cm- l

cm- l

(Gas) 2782.5 S 1746.1 VS 1500.1 S 2843.1 VS 1249.1 S 1167.3 S

(Gas) 2781.6 1742.3 1499.7 2866

S W M W

I

I

I

Comments

I

\

References [1] R. [2] IR. [3] IR. [4] IR.Th.

D. H. K. T.

W. Davidson, B. P. Stoicheff, and H. J. Bernstein, J. Chern. Phys. 22, 289 (1954). H. Blau, Jr. and H. H. Nielsen, J. Mol. Spectrosc. 1, 124 (1957). B. Harvey and J. F. Ogilvie, Can. J. Chern. 40, 85 (1962). Nakagawa, H. Kashiwagi, H. Kurihara, and Y. Morino, J. Mol. Spectrosc., 31, 436 (1969).

Molecule: Formaldehyde-d l HDCO Symmetry C s Symmetry number d

Sym. species

No.

a'

VI V2

Va

a" I

I

V4 V5 V6

Approximate type of mode

CH stretch ............. CD stretch ............. CO stretch ............. CHD scis., ............. CHD rock .............. CHD wag .............. t

No. 69 1

Selected value of frequency

Infrared

2844 D 2121 D 1723 A 1400 B 1041 D 1074 C

Raman

cm- l

cm- l

(Gas) 2844.1 S 2120.7 S 1723.4 VS 1400.0 S 1041 S 1074 S

(Gas) 2846.2 S 2120.3 S 1723.2 VS 1397.4 M

I

Reference [1] IR.R.

D. W. Davidson, B. P. Stoicheff, and H. J. Bernstein, J. Chern. Phys. 22, 289 (1954).

44

Comments

+ V5).

FR (va FR (2V6'

2V5).

Molecule: Forlllaldehyde-d2 D 2CO SYlllllletry C2v SYlllllletry nUlllber d

Syn;t. speCIes

Approximate type of mode

No.

VI

al

V2

Va hI

V4 V5

CD 2 s-stretch ........... CO stretch ............. CD 2 scis ................ CD 2 a-stretch ........... CD 2 rock ............... \ CD 2 wa g ............... \

No. 70 2

Selected value of frequency

Infrared

Raman

cm- 1

cm- I

Comments

(Gas) 2056.4 S ............ FR (2va). 1700 VS 1106.0S 2160.3 VS 990.2 S 938 S

2056 D 1700 B 1106 C 2160 C 990 C 938 E

Reference [1] IR.

E. S. Ebers and H. H. Nielsen, J. Chem. Phys. 6, 311 (1938).

Molecule: Methane SYlllllletry T d

Syn;t. speCIes

No.

al

VI

e

V2

/2

Va V4

a

CH 4

No. 71

12

SYlllllletry nUlllber d

Approximate type of mode

Sym. stretch ............ Deg. deform ............ Deg. stretch ............ Deg. deform ............

Selected value of frequency

V4

Raman

cm- 1 (~as)

cm- I

Ia ia, a1533 3018.9 1306.2

2917 A 1534 A 3019 A 1306 C

Observed in the infrared through Coriolis interaction with

Infrared

Comments

(Gas) 2917.0 1533.6 3019.5

[5].

References [1] [2] [3] [4] [5]

IR.R. IR. R. R. IR.

G. Herzberg, Infrared and Raman Spectra of Poly atomic Molecules (Van Nostrand, New York, 1945). H. C. Allen, Jr., and E. K. Plyler, J. Chem. Phys. 26,972 (1957). M. A. Thomas and H. L. Welsh, Can. J. Phys. 38, 1291 (1960). J. Herranz and B. P. Stoicheff, J. Mol. Spectrosc. 10, 448 (1963). J. Herranz, J. Morcillo, and A. Gomez, J. Mol. Spectrosc. 19, 266 (1966).

45

Molecule: Methane-d l SYInInetry C 3v

Sym. species

No.

CH 3D

No. 72 3

SYInInetry nUInber d

Approximate type of mode

Selected value of frequency

Infrared

cm- l al

VI

CH 3 s-stretch ...........

2945 E

V2

e

V3 V4

CD stretch ............. CH 3 s-deform ........... CH 3 d-stretch ........... CH 3 d-deform CH 3 rock ...............

2200 1300 3017 1471 1155

Vs

I

I

V6

(Gas) f2973 \2914 2200.0 1300 3016.9 ]471 1155

A C B C C

I

Raman

Comments

cm- l

(Gas)

M M M M S

~I

}...........

FR (2vs).

1306 1156

II 1

References [1] IR.R.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York, 1945), and references cited there. J. K. Wilmhurst and H. J. Bernstein, Can. J. Chern. 35, 226 (1957). H. C. Allen, and E. K. Plyler, J. Res. NBS 63, 145 (1959). L. H. Jones, J. Mol. Spectrosc. 4, 86 (1960).

[2] IR. [3] IR. [4] IR.

Molecule: Methane-d2 SYInInetry C 2v

Sym. species

No.

Selected value of frequency

CH 2 s-stretch ........... CD 2 s-stretch ........... CH 2 scis ................ CD 2 scis ................ CH 2 twist .............. CH 2 a-stretch ........... I CH 2 rock ............... I CD 2 a-stretch ........... I CH wag ............... 2

Observed in the infrared through Coriolis interaction with

JIg.

V3 V4

Vs

a2

I

Approximate type of mode

C C C C C C C C C

V2

I

No. 73 2

2974 2202 1436 1033 1333 3013 1090 2234 1234

VI

al

!

CH2D 2 SYInInetry nUInber d

bl

V6 V7

b2

Vs V9

I

Infrared

cm- 1 (Gas) 2976M 2202W 1436W 1033 S ia, a1329 W 3013 S 1090S 2234M 1234M

Raman

Comments

cm- l

(Gas) 2974 1034 1333 1090

I a

References [1] IR.R.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York,-!945), and refer-

[2] IR.

ences cited there. J. K. Wilmshurst and H. J. Bernstein, Can. J. Chern. 35, 226 (1957).

46

Molecule: Methane-d s Symmetry C sv

Sym. species

Approximate type of mode

No.

V2

Vs e

V4 V5 V6

i

I

No. 74 3

Selected value of frequency

2993 C 2142 C 1003 C 2263 C 1291 C 1036 C

CH stretch ............. CDs s-stretch ........... CD s s-deform ........... CDa d-stretch ........... CDs rock ............... CDs d-deform ...........

VI

UI

CHDs Symmetry number d

Infrared

Raman

cm- I (Gas)

cm- I (Gas)

2993 M 2142 M 1003 M 2263 M 1291 M 1036 S I

I

Comments

2141 2269 1299 1046 I

;

I

I

References See No. 73.

Molecule: Methane-d 4 CD 4 Symmetry number d Symmetry Td

Sym. species

No.

Selected value of frequency

2109 1092 2259 996

B B

Observed in the infrared through Coriolis interaction with

P4

UI e

V2

/2

Vs

VI V4

I a

Approximate type of mode

Sym. stretch ............ Deg. deform ............ Deg. stretch ............ Deg. deform ............

No. 75

12

Infrared

Raman

cm- I

cm- I (Gas)

(~as)

la ia, a1092

2259.3 996.0

A

B

Comments

2108.9 1091.9 2259.3

[5].

References [1] IR.R.

[2] [3] [4] [5]

IR. R. R. IR.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York, 1945), and references cited there. H. M. Kaylor and A. H. Nielsen, J. Chern. Phys. 23, 2139 (1955). G. C. Shepherd and H. L. Welsh, J. Mol. Spectrosc. 1, 277 (1957). R. A. Olafson, M. A. Thomas, and H. L. Welsh, Can. J. Phys. 39, 419 (1961). H. Herranz, J. Morcillo, and A. Gomez, J. Mol. Spectrosc. 19, 266 (1966).

47

Molecule: Carbon tetraHuoride CF 4 SYlllllletry T d SYlllllletry nulllber d

Sym. species

Selected value of frequency

Approximate type of mode

No.

No. 76

12

Infrared

Raman

cm- I al

VI

e

V2 V3

12

632 B

Deg. deform ............

V4

I

I

cm- I

(Gas) ia la 1282.6 VS 1260.9 VW 631.73 VS

909 B 435 B 1281 D

Sym. stretch ............ Deg. deform ............ Deg. stretch ............

(Gas) 908.5 S 435.0 S 1283.0 W FR 1263 VW 631.2 S

(2V4).

I

I

I

I

Comments

References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10]

D. M. Yost, E. N. Lassettre, and S. T. Gross, J. Chern. Phys. 4, 325 (1936). C. R. Baeley, J. B. Hale, and H. W. Thompson, Proc. Roy. Soc. (London), Ser. A, 167, 555 (1938). E. K. Plyler and W. S. Benedict, J. Res. NBS 47, 202 (1951), RP 2245. P. J. H. Woltz and A. H. Nielsen, J. Chern. Phys. 20, 307 (1952). W. F. Edgell and R. E. Moynihan, J. Chern. Phys. 27, 155 (1957). B. Monostri and A. Weber, J. Chern. Phys. 33, 1867 (1960). S. Abramowitz and R. Bauman, Spectrochim. Acta 17, 127 (1961). A. Maki, E. K. Plyler, and R. Thibault, J. Chern. Phys. 37, 1899 (1962). S. Abramowitz and R. Bauman, J. Chern. Phys. 39, 2757 (1963). A. A. Chalmers and D. C. McKean, Spectrochim. Acta 22, 251 (1966).

R. IR. IR.Th. IR. IR.Th. R. IR. IR. IR. IR.

Molecule: Carbon tetrachloride CCl 4 SYlllllletry T d SYlllllletry nulllber d

Sym. species

Approximate type of mode

No.

Selected value of frequency

al

VI

e

V2 V3

Sym. stretch ............ Deg. deform ............ Deg. stretch ............

459 C 217 C 776 E

V4

Deg. deform ............

314 C

12 I

I

No. 77

12

{ [

I

Infrared

Raman

cm- I (~as)

cm- I

(Liquid) la 458.7 (10) p la 217.0 (7) dp 789 VS 790.4 (4) dp }FR 768 VS 761.7(4) dp 309.9 W 313.5 (9) dp (liquid)

Comments

(VI

+ V4).

I

References [1] IR.R. [2] R. [3] IR. [4] IR. [5] IR.

[61 R. [7] R.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York, 1945).

J. P. Zietlow, F. F. Cleveland, and A. G. Meister, J. Chern. Phys. 18, 1076 (1950). J. R. Madigan and F. F. Cleveland, J. Chern. Phys. 19, 119 (1951). E. K. Plyler and W. S. Benedict, J. Res. NBS 47, 202 (1951), RP2245. H. Yoshinaga, J. Chern. Phys. 23, 2206 (1955).

D. A. Long, D. C. Milner, and A. G. Thomas, Proc. Roy. Soc. (London), Ser. A, 240, 499 (1957). M. Ito, Spectrochim. Acta 21, 731 (1965).

48

l\'Iolecule: Carbon tetrabromide CBr 4 Sym.m.etry Td Sym.m.etry num.ber d

Sym. species

Approximate type of mode

No.

No. 78

12

Selected value of frequency

Infrared

Raman

Comments

cm- 1 (Liquid)

al

VI

e

V2

/2

V3 V4

Sym. stretch ............ Deg. deform ............ Deg. stretch ............ Deg. deform ............

267 122 672 182

cm- 1 (Benzene soln.) la 267 (7) p la 122 (10) dp 671 (1) dp 672 VS ........... 182 (4) dp

C C C C

References [1] [2] [3] [4]

IR.R. R. IR.R. R.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York, 1945). A. G ..Meister, S. E. Rosser, and F. F. Cleveland, J. Chern. Phys. 18, 346 (1950). E. K. Plyler, W. H. Smith, and N. Acquista, J. Res. NBS 44, 503 (1950), RP2097. D. A. Long, D. C. Milner, and A. G. Thomas, Proc. Roy. Soc. (London), Sere A, 240, 499 (1957).

No. 79

l\'Iolecule: Carbon tetraiodide CI 4 Sym.m.etry T d Sym.m.etry num.ber d

Sym. species

Approximate type of mode

No.

al

VI

e

1'2

/2

V3 V4

Sym. stretch ............ Deg. deform ............ Deg. stretch ............ Deg. deform ............

r

12

Selected value of frequency

178 90 555 125

D D D E ,

I a

Infrared

Raman

cm-1 (S