Vibrational Spectra of OsF6 and PtF6

Bernard Weinstock, Howard H. Claassen, and John G. Malm

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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 SPIN DENSITIES IN HYDROCARBON RADICALS 181

and J'COK = - (!)''\KOKO,

n
AK, thus bK/ aK, is a positive quantity because of posi-
PB(r) = (N")-!( LCd[ -{(b i/a;)2+Hb;/ai)2
i=l tive value which .\KoKO must have.
Inclusion of different O/s has the effect of weighing
-((b;/ai)3_t(b;/a;) L(bj/aj)2JlXB2(r). (16) the excited configurations differently, which is cer-
,>j
tainly the more reasonable case. We note that the
To determine the sign of b;/ai the same type of conclusion of negative spin density at the unstarred
argument as proposed in the text can be applied. atom is still valid in this more general treatment.
n However, in this approximation the spin density at
'¥oround.t.te=lfo+ LAKlfK' different unstarred atoms is not the same. Unfortu-
K~l
nately no experimental results are 'available for the
where case of proton-electron coupling on more than one
unstarred carbon atom.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 32, NUMBER 1 JANUARY, 1960

Vibrational Spectra of OsF 6 and PtF 6 *

BERNARD WEINSTOCK, HOWARD H. CLAASSEN,t AND JOHN G. MALM

Argonne National Laboratory, Lemont, Illinois

(Received July 28, 1959)

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.

INTRODUCTION ent paper the vibrational spectra of OsF 6 and PtF6,

HE characteristic volatility of the inorganic hexa-
T fluorides offers the possibility for the study of the
behavior of nonbonding electrons in molecular environ-
ments of well-defined symmetry. In the vapor phase
where molecular distortions due to neighboring mole-
cules are largely avoided, these compounds have been
found to have the high symmetry of the octahedral
point group Ok. There is the interesting possibility,
however, that a distortion due to the Jahn-Teller effect
can arise for those compounds in which the nonbonding
electrons produce degenerate ground states.!
In the infrared spectra of NpF6 and PuF 6, which we.
previously reported,2 no evidence for distortion of the
molecular configuration due to the nonbonding 5f
electrons in these molecules was apparent. In the pres-
* Based on work performed under the auspices of the U. S.
Atomic Energy Commission.
t Permanent address, Wheaton College, Wheaton, Illinois.
I H. A. Jahn and E. Teller, Proc. Roy. Soc. (London) AtM,
220 (1937).
2 MaIm, Weinstock, and Claassen, J. Chern. Phys. 23, 2192
(1955) .
which contain two and four non bonding 5d electrons,
respectively, are reported. This study of OsF 6 contri-
buted to the demonstration that the volatile yellow
fluoride of Os is actually a hexafluoride and not the
unique octafluoride that it had been erroneously called
during the forty years since its first preparation. 3 Also,
these infrared measurements with the recently prepared,
volatile, red fluoride of Pt 4 supported its identification
as a hexafluoride molecule and consequently as the only
known hexavalent compound of Pt.
EXPERIMENTAL TECHNIQUE
The compounds were prepared by the reaction be-
tween fluorine gas and the metals at elevated tempera-
tures; the details of the preparation and purification
are given elsewhere. 3.4
The infrared absorption spectra of OsF 6 and PtF6
3 B. Weinstock and J. G. MaIm, J. Am. Chern. Soc. 80, 4466
(1958) .
4 Weinstock, Claassen, and MaIm, J. Am. Chern. Soc. 79, 5832
(1957) .

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 182 WEINSTOCK, CLAASSEN, AND MALM

were studied using a Model 21 Perkin-Elmer spectro-

photometer from 4000 to 400 cm- I with NaCI and KBr
optics and a Beckman IR-4 spectrophotometer from
1000 to 300 cm-I with CsBr optics. The range from 350
to 200 cm-I was studied with a grating spectrometer D FIG. 1. Infrared
at Ohio State University. We are indebted to Dr. R. A. spectrum of OsF 6
Oetjen for the use of this far infrared spectrograph5 E vapor (cell length,
10.3 em) using NaCl
and to his students, Miles Vance and Raymond Brown, prism from 1500 to
for their help in obtaining the spectra. 650 em-I, CsBr from
z 450 to 300 em-I, and
Two I-in. i.d. absorption cells were used: a nickel cell, o f-16,L0:-:0'--'-1-:-40'::-0=---:-:12,L0-0-l-:-00LO~-::8,L0.l.\.0.JL.6-:-0LO::----lgrating from 300 to
I-
10.3 cm long and fitted either with AgCl or with poly- a. 250 em-I. The sam-
0::
ethylene windows, and a brass cell 11.0 cm long with o ~ pIe pressures were:
(/) - 40~ .'!. \~ A (background), B
BaF2 windows. The BaF2 windows were very brittle (IJ
364 (5mm),C (13mm),
«
and cracked upon the application of even slight pres- D (90 mm), E (300
sure against soft gasket materials. For this reason mm), and F (600
mm). The cell was
the windows were cemented to the cell with a thermal at room tempera-

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

nearly matches that of CaF 2, which in turn has physical

properties close to those of BaF2.
Considerable difficulty was encountered in obtaining
the spectra because of attack or deposition on the win-
dow materials. In general, BaF2was found to be superior
to AgCI out to its practical cutoff frequency of 800
cm-I . Although both hexafluorides are strong fluorinat-
ing agents, polyethylene was again successfully used
as the window material in the region 450 to 200 cm-I
as had been done with CIF 3 .6 It was therefore not neces-
sary to use KRS-5 windows, which show rapid attack
by other hexafluorides. 2
The Raman spectrum of liquid OsF6 was obtained
using a Hilger E612 spectrograph with 1/6.3 camera
and Eastman 103 a- C plates. Excitation was by the
5461A line from a water cooled mercury arc filtered
by a 3-cm thickness of 13 wt % aqueous Na2Cr04. The
filtering solution and sample tube were kept about five
degrees above the melting point of OsF6, 32°C. Exposure
times were 15,45, and 150 min. The green Hg line was
used rather than the blue in order to minimize possible
photochemical decomposition of the yellow liquid.
The sample tube for the Raman experiment consisted
of a 2-cm length of 6-mm o.d. Pyrex tubing with a plane
window that contained the liquefied sample during the
irradiations. Joined to this was a 10-cm length of 12-mm
tubing that was used to condense the sample during
the filling and served as a ballast volume for possible
fluorine pressure build-up arising from photochemical
decomposition. The concern about photochemical
decomposition was a consequence of our experiences
with NpF6 and PUF6 where the photochemical decom-
position even with the vapor was too severe to allow a
• Oetjen, Haynie, Ward, Hansler, Schauwecher and Bell, J.
Opt. Soc. Am. 42,559 (1952).
6 Claassen, Weinstock, and MaIm, J. Chern. Phys. 28, 285
(1958) .
400 360 280 250
study of the Raman effect.2 However, OsF6, in spite of
its yellow color in the liquid phase, appeared to be
relatively insensitive to photochemical decomposition. 7
No attempt was made to obtain the Raman spectrum of
the intensely colored dark red PtF6.
SPECTRA AND INTERPRETATION
Two Raman bands were observed for OsF6 shifted
252 and 733 cm-1 from the exciting line. The former is
clearly visible on the IS-min. exposure where the latter
is barely seen, and the 733-cm-1 band appears clear
and sharp on the 45-min exposure where the 252-cm- 1
is hidden in the high background near the exciting line.
It is difficult to make even a qualitative estimate of
relative intensities because the sample absorbs in the
visible and because of the high background at the 252-
cm-1 band. Although the third Raman-active funda-
mental would lie in a favorable region for observation,
it is neither observed in these exposures nor in a 150-
min. exposure and therefore it is clearly weaker or
much more diffuse than those observed.
The tracings of the infrared spectra are shown in
Figs. 1 and 2. These were obtained only after much
difficulty because of the reactive nature of the com-
pounds under study. Two kinds of spurious absorption
bands resulted, one due to nonvolatile deposits on the
window and the other to contamination of the gas with
volatile reaction products. This seasoning of the cell
eventually ceased or became very Blow so that it was
possible to interpret the spectra reliably. To avoid
false interpretations due to window deposits no spec-
7 The 1.5-g sample of OsF6 used for the Raman experiment was
quantitatively recovered about a year later; the upper limit of
photochemical decomposition was estimated to be 0.3%.

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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
cations of their theory,18-23 however, none have detailed
the type of effect in the rotation-vibration spectra
described in the foregoing.
Of the eleven hexafluorides for which vibrational
spectra have been reported in sufficient detail, only
ReF6 and OsF6 have the appropriate electronic de-
generacy to participate in the Jahn-Teller effect.
ReF6 and OSF6 contain 5d1 and 5d2 nonbonding elec-
tronic configurations which give rise to fourfold and
fivefold degenerate ground states, respectively.12 SF6,
SeF6, MoF6, TeF6, WF6, and UF6 use all of their valence
electrons in the six bonding orbitals of the molecule
and therefore have nondegenerate electronic ground
states. For PtF612 and PUF624 which have 5d 4 and 5]2
nonbonding electronic configurations, respectively, the
degeneracy of the ground state is removed under the
influence of the octahedral ligand field. For NpF625
with a 5j! configuration the ground state is a Kramers
doublet which does not participate in the Jahn-Teller
effect. IrF6 also has a degenerate electronic ground state
capable of showing a Jahn-Teller coupling but its spec-
tra have not been reported in sufficient detail to be
discussed. to
18 J. It Van Vleck, ]. Chern. Phys. 7 61, 72 (1939).
19U. Opik and M. H. L. Pryce, Proc. Roy. Soc. (London)
A238,425 (1957).
20 Longuet-Higgins, eJpik, Pryce, and Sack, Proc. Roy. Soc.
(London) A244,1 (1958).
21 W. Moffitt and A. D. Liehr, J. Chern. Phys. 25,1074 (1956);
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).
24 Gruen, MaIm, and Weinstock, ]. Chern. Phys. 24, 905 (1956).
25 G. L. Goodman and M. Fred, ]. Chern. Phys. 30, 849 (1959).
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6 AND PtF 6 185
Thus, since only ReFa and OsF6 have suitable de-
generate ground states it appears very likely that the
distinct behavior of 0"2 and its binary combination
bands for these molecules is a consequence of the Jahn-
Teller effect. This conclusion is substantiated by the
fact that 0"2 has the symmetry eo, which was predicted to
result in a nonvanishing contribution to the first-order
perturbation energy for point group Oh to which the
hexafluorides belong.t This observation is in agreement
with the view first detailed by Van Vleck18 and since
developed by several others that the Jahn-Teller effect
for nonbonding electrons need not evidence itself by a
static distortion but rather may appear as a special
vibronic coupling. It is also significant that 0"6, the vibra-
tion of symmetry 120' may give rise to similar linear
terms in the potential energy but according to these
experimental observations the effect is much smaller
than that of the eo vibration in ReF6 and OsFa.
FORCE CONSTANTS
When the force constant calculations for hexa-
fluorides26 were done, 0"6 for OsF6 had not yet been
definitely located and several force constants were left
out. With the present value of 230 cm-1 for 0"6 we
obtain
1a-'Y- 2K+2f=0.296md/A,
1a - 'Y = 0.299 md/A, 1a a - 'Y = +0.053 md/ A, and
K-f=+O.OO2 md/A.
26 H. H. Claassen, ]. Chern. Phys. 30, 968 (1959).