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Weinstock 1960
Weinstock 1960
Citation: The Journal of Chemical Physics 32, 181 (1960); doi: 10.1063/1.1700895
View online: http://dx.doi.org/10.1063/1.1700895
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Timeofflight neutron powder diffraction study on the third row transition metal hexafluorides WF6, OsF6,
and PtF6
J. Chem. Phys. 104, 7658 (1996); 10.1063/1.471473
Theoretical study of the vibrational spectra of the transition metal carbonyls M(CO)6 [M=Cr, Mo, W],
M(CO)5 [M=Fe, Ru, Os], and M(CO)4 [M=Ni, Pd, Pt]
J. Chem. Phys. 102, 8474 (1995); 10.1063/1.468839
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SPIN DENSITIES IN HYDROCARBON RADICALS 181
Infrared absorption spectra of gaseous OsF. and PtF. from 6-501' and the Raman spectrum of liquid
OsF. are reported. These are interpreted in terms of the octahedral point group Ok, and the six funda-
mental frequencies are determined. Their values and symmetry species are for OsF. 733 (al g ) , 632 (e g ) , 720
(flu),268 (f,u), 252 (f2g), and 230 (f2u); for PtF. 655 (a, g) , 601 (e g) , 705 (f,u), 273 (flu), 242 (f2g) , and 211
(f2u). Thermodynamic functions, including electronic contributions, are calculated for the ideal gaseous state
of both compounds.
A comparison of the details of the vibrational spectra of eleven hexafluorides reveals certain charac-
teristic features for OsF. and ReF•. Since only these two molecules have appropriately degenerate elec-
tronic ground states these differences are interpreted as evidence of a J ahn-Teller effect.
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182 WEINSTOCK, CLAASSEN, AND MALM
c~
setting Araldyte resin. The resin was set by maintaining ture except for F
when it was main-
it overnight at 140°C. To prevent cracking of windows tained at 45°C.
due to unequal thermal contraction upon cooling, a thin-
walled (-i2 in.) metal tube was used. Brass was chosen
rather than Ni because its expansion coefficient more 268
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VIBRATIONAL SPECTRA OF OsF. AND PtF" lR3
tral scan was taken as reliable unless the background TABLE 1. The vibrational spectra (cm-I ).
scan was the same before and after the sample scan.
For example in the PtF6 spectrum shown in Fig. 2 the OsF6 PtF.
large background absorptions between 500-700 cm-l Observed Calculated Observed Calculated Assignment
and 1100-1200 cm-l resulted from the initial exposure
of the gas to the windows but did not sensibly alter 252 (Raman) u,
during the further measurements. The absorption 268 S
269}
273 VS U4
bands due to the volatile impurities were identified in 278
the course of increasing the sample pressure by raising 364 VW 364 328 U'l-0'4
402VW 402 390 VW 390 0"2-0"6
the temperature of the condensed phase in the side- 720 VS 705 VS us
arm; a point being reached where the intensity of the 733 (Raman) UI
spurious bands increased very little while the sample 862 812 W 812 U2+ U•
894 VW 900 869 W 874 U2+U4
bands continued to increase. It was possible to obtain 969W 972 947W 947 U3+ U6
spectra that were free from this type of impurity by 1268 VW 1256 1250 VW 1251 2U4+U3
1352 W 1352 1306M 1306 U,+U3
repeated seasoning of the cell and repurification of the 1453 M 1453 1360M 1360 0"1+0"3
samples by vacuum fractional sublimation. The spec-
tra shown in Figs. 1 and 2 are believed to be representa-
tive of the pure compounds. An uncertainty remains series hexafluorides, WF6,8 ReF6,9 and IrF6,1O and on
for some very weak absorption bands observed for this basis the spectra are interpreted successfully in
OsF6 at 325, 352, 544, 644, and 800 cm- l . These were terms of the structure of a regular octahedron, point
observed in scans other than those shown in Fig. 1 group Oh. The infrared-active binary combinations for
and although they very likely are due to impurities molecules of this type are tabulated in reference 8.
they cannot be ruled out with certainty because of The two infrared-active fundamentals 0'3 and 0'4 are
easily recognized because of their great intensity. Two
their weakness.
moderately strong bands for both OsF6 and PtF6 at
The main features of the spectra for OsF6 and PtF6
roughly twice the frequency of 0'3 can be assigned un-
are similar to those observed for the other 5d transition ambiguously as 0'1+0'3 and 0'2+0'3 and serve to locate
0'1 and 0'2. Similarly, 0'5 can be evaluated for both from
the sum band 0'3+0'5. For OsF6 both 0'1 and 0'5 thus
obtained agree well with the values obtained directly
in the Raman spectrum. For PtF6, 0'6 can be located
from the binary combination 0'2+0'6 as well as from the
corresponding difference band. The sum band 0'2+0'6
was not observed in OsF 6 and although the difference
band was observed it was necessary to heat the cell
above room temperature. Although the failure to ob-
serve 0'2+0'6 for OsF6 may in part be due to its proximity
z to the strong fundamental 0'3 we shall presently offer
~ another explanation.
I-
a. The observed vibrational frequencies of OSF6 and
a:: 1200 1000 800
0
en PtF6, their assignments, and the calculated values for
(II
« 705 the combination bands are listed in Table 1. In Table
=-v.JF II are listed the derived fundamental frequencies as
I
390 well as their spectral activity and symmetry species.
THERMODYNAMIC PROPERTIES
~
The thermodynamic properties of OsF6 and PtF 6 in
D the ideal gaseous state at one atmosphere pressure from
C 273 250 to lOOOoK are given in Tables III and IV, respec-
tively. These have been calculated by means of statisti-
278 269 cal mechanics with the usual approximations and in-
600 400 300 200 clude contributions from the excited electronic . levels
FIG. 2. Infrared spectrum of PtF. vapor (cell length, 10.3 cm), as well as from the degeneracy of the ground state.
using NaCl prism from 1500 to 800 cm-I, KBr from 750 to 375
cm-I, and grating from 300 to 250 em-I. The sample pressures 8 Burke, Smith, and Nielsen, J. Chern. Phys. 20, 447 (1952).
were: A (background), B (1 mm), C (20 mm), D (27 mm), E 9 J.
Gaunt, Trans. Faraday Soc. 50, 209 (1954).
(110 mm), F (240 mm), and G (370 mm). The cell was at room 10 Mattraw, Hawkins, Carpenter, and Sabol, J. Chern. Phys.
temperature except for F and G when it was maintained at 50°C. 23,985 (1955).
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184 WEI N S T 0 C K, C L c\ ASS EN, AND MAL ~r
TABLE II. Fundamental vibrational frequencies (em-I). is derived for the other hexafluorides was not observed.
Furthermore, detailed comparisons of the vibrational
Symmetry Spectral spectra show that for OsF. the vibration of symmetry
Designation species activity OsF6 PtF6
eg, 0"2, and its other allowed binary sum bands appear
0"1 alu Raman,p 733 655 to be less intense or markedly broader than in the cor-
0"2 eo Raman, dp 632 601 responding bands for nine other hexafluorides SF6 ,
0"3 flU Infrared 720 705 SeF6, MoF 6, TeF6 , WF6, UF6, PtF6, NpF6, and
0", fl,. Infrared 268 273 PuF6.2.8.16,16 Thus, 0"2 was not observed in the Raman
0"5 f2g Raman, dp 252 242
0"6 f2u Inactive 230 211 effect under conditions where 0"1 and 0"6 were observed
whereas 0"2 is usually more easily observed than 0"5
because of the latter's proximity to the exciting line.
For OsF6 the following data were used: molecular In addition, 0"2+0"4 is so weak as to be uncertain and
weight 304.2 on the chemical scale; Os- 1" distance, 0"2+0"3, although intense, is greatly broadened. This
1.831 A;ll and the pertinent electronic states a fivefold broadening of 0"2+0"3 is particularly noteworthy because
degenerate ground state, a singlet level at 3900 cm-1 and a characteristic feature of the infrared spectra of the
a triplet level at 4300 cm-1.12 For PtFs the data were: above mentioned nine hexafluorides is the fact that
molecular weight, 309.09;13 Pt- F distance (extrapo-
lated from values for WFs, OsF6, and IrF6)1l 1.829 A; TABLE IV. Thermodynamic properties of PtFs in the ideal
and the pertinent electronic states a non degenerate gaseous state at one atmosphere pressure.
ground state, a triplet at 3300 cm-1 and a quintet at
5500 cm-l.12 The fundamental constants used in these T Cpo - (PO-EoO)/T So (HO-EoO)
calculations were taken from the American Petroleum cal mo\e-1 cal mo\e-1 cal mole- 1
Institute tabulation. 14 For OsF6 the contribution to the OK deg-1 deg-1 deg-1 cal mole- 1
entropy due to the degeneracy of the ground state is
Rln5=3.198 cal mole-I deg-1; the contribution due to 250 27.222 60.923 78.180 4314.2
the excited electronic levels at lOOOoK is 0.028 cal 273.15 28.312 62.490 80.639 4957.4
298.15 29.355 64.119 83.165 5678.6
mole-1 deg- 1 additionally. For PtF6 the ground state is 350 31.080 67.306 88.013 7247.6
non degenerate and makes no contribution to the en- 400 32.330 70.164 92.250 8834.2
tropy; the contribution from the excited electronic 500 34.046 75.343 99.663 12160
600 35.175 79.935 105.976 15625
levels is 0.321 cal mole- l deg- 1 at lOOOoK. 700 36.026 84.057 111.465 19186
800 36.750 87.792 116.324 22825
JAHN-TELLER EFFECT 900 37.410 91.209 120.689 26534
1000 38.027 94.360 124.665 30306
As previously mentioned, 0"6, the frequency of the
inactive fundamental vibration, was difficult to evalu-
ate for OsF6 because the sum band 0"2+0"6 from which it 0"2+0"3 appears close to 0"1+0"3 with almost identical
intensity and shape as seen for example for PtF6 in
TABLE III. Thermodynamic properties of OsF6 in the ideal
gaseous state at one atmosphere pressure. Fig. 2. The one other exception in which 0"2+0"3 is
broadened in a similar way to OSF6 is found with ReFs.9
T Cpo - (PO-EoO)/T SO (HLEoO) In the Raman effect for ReF6 , 0"2 is observed but is
broadened compared to its shape when observed with
cal mole-1 cal mole-1 cal mo\e- l cal mole-1
OK deg-1 deg-1 deg-1 other hexafluorides.
This distinctive behavior of 0"2 and its binary sum
250 26.711 63.782 80.658 • 4219.0 bands for ReFs and OsF6 is believed to be a consequence
273.15 27.825 65.315 83.073 4850.5 of the Jahn-Teller effect,l7 Jahn and Teller! showed by
298.15 28.880 66.909 85.556 5559.6 group theoretical arguments that orbital electronic
350 30.657 70.031 90.332 7105.3
400 31. 955 72.834 94.514 8672.0 degeneracy in nonlinear polyatomic molecules would
500 33.728 77.925 101.852 11964 result in an instability in the structural configuration
600 34.830 82.447 108.106 15396
700 35.558 86.510 113.534 18918 and as a consequence the molecules would distort their
800 36.073 90.192 118.318 22500 structure to one of lower symmetry in order to remove
900 36.457 93.558 122.589 26128 this degeneracy. For nonbonding electrons, as will be
1000 36.761 96.644 126.431 29786
the case for the hexafluorides, it was suggested that the
inherent instability due to orbital degeneracy would be
11 Schomaker, Kimura, Smith, and Weinstock (unpublished less severe. Since the original papers of Jahn and Teller
results) .
12 Moffitt, Goodman, Fred, and Weinstock, Mol. Phys. 2, 109 there have appeared numerous extensions and amplifi-
(1959).
13E. Wichers, J. Am. Chern. Soc. 78, 3235 (1956). 15 Yost, Steffens, and Gross, J. Chern. Phys. 2, 311 (1934).
14Rossini, Pitzer,.Arnett, Braun, and Pimentel, Selected Values 16 J.
Gaunt, Trans. Faraday Soc. 49, 1122 (1953).
of Physical and Thermodynamic Properties of Hydrocarbons and 17 B. Weinstock and H. H. Claassen, J. Chern. Phys. 31, 262
Related Compounds (Carnegie Press, Pittsburgh, 1953). (1959) .
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VIBRATIONAL SPECTRA OF OsF 6 AND PtF 6 185
cations of their theory,18-23 however, none have detailed Thus, since only ReFa and OsF6 have suitable de-
the type of effect in the rotation-vibration spectra generate ground states it appears very likely that the
described in the foregoing. distinct behavior of 0"2 and its binary combination
Of the eleven hexafluorides for which vibrational bands for these molecules is a consequence of the Jahn-
spectra have been reported in sufficient detail, only Teller effect. This conclusion is substantiated by the
ReF6 and OsF6 have the appropriate electronic de- fact that 0"2 has the symmetry eo, which was predicted to
generacy to participate in the Jahn-Teller effect. result in a nonvanishing contribution to the first-order
ReF6 and OSF6 contain 5d1 and 5d2 nonbonding elec- perturbation energy for point group Oh to which the
tronic configurations which give rise to fourfold and hexafluorides belong.t This observation is in agreement
fivefold degenerate ground states, respectively.12 SF6, with the view first detailed by Van Vleck18 and since
SeF6, MoF6, TeF6, WF6, and UF6 use all of their valence developed by several others that the Jahn-Teller effect
electrons in the six bonding orbitals of the molecule for nonbonding electrons need not evidence itself by a
and therefore have nondegenerate electronic ground static distortion but rather may appear as a special
states. For PtF612 and PUF624 which have 5d 4 and 5]2 vibronic coupling. It is also significant that 0"6, the vibra-
nonbonding electronic configurations, respectively, the tion of symmetry 120' may give rise to similar linear
degeneracy of the ground state is removed under the terms in the potential energy but according to these
influence of the octahedral ligand field. For NpF625 experimental observations the effect is much smaller
with a 5j! configuration the ground state is a Kramers than that of the eo vibration in ReF6 and OsFa.
doublet which does not participate in the Jahn-Teller
FORCE CONSTANTS
effect. IrF6 also has a degenerate electronic ground state
capable of showing a Jahn-Teller coupling but its spec- When the force constant calculations for hexa-
tra have not been reported in sufficient detail to be fluorides26 were done, 0"6 for OsF6 had not yet been
discussed. to definitely located and several force constants were left
18 J. It Van Vleck, ]. Chern. Phys. 7 61, 72 (1939). out. With the present value of 230 cm-1 for 0"6 we
19U. Opik and M. H. L. Pryce, Proc. Roy. Soc. (London) obtain
A238,425 (1957).
20 Longuet-Higgins, eJpik, Pryce, and Sack, Proc. Roy. Soc. 1a-'Y- 2K+2f=0.296md/A,
(London) A244,1 (1958).
21 W. Moffitt and A. D. Liehr, J. Chern. Phys. 25,1074 (1956); 1a - 'Y = 0.299 md/A, 1a a - 'Y = +0.053 md/ A, and
Phys. Rev. 106, 1195 (1957).
22 W. Moffitt and W. Thorson, Phys. Rev. 108, 1251 (1957).
23 A. D. Liehr and C. ]. Ballhausen, Ann. Phys. 3, 304 (1958).
K-f=+O.OO2 md/A.
24 Gruen, MaIm, and Weinstock, ]. Chern. Phys. 24, 905 (1956).
25 G. L. Goodman and M. Fred, ]. Chern. Phys. 30, 849 (1959). 26 H. H. Claassen, ]. Chern. Phys. 30, 968 (1959).
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