chcmiul Physics 91(19s4) 113-118

North-Holland. Amsterdam
RAMAN SPECIROSCOPY OF THE ITeX,]- IONS (x = CI OR Br)
AT RESONANCE WITH THEIR LOWEST 3T,I. AND Tr,, STATES:
EVIDENCE FOR TETRAGONAL DISTORTION IN THESE EXCITED STATES
Robin J-H_ CLARK and Martin J_ STEAD
Chri stopher Inp/d Labswatori a, Uni _coszp C02ese Landon. 20 Gordon Screr. London MCIH OAJ . LX
Rec c i t d 21 May 1%
The obscn~tion &at xhht w&) band is tbc most entunced
T,. - A,, and IT,,, - A,=
Raman band at msonzsncc with the bands assigned to both the
transitions of Ihe ~eX,l- ions indicates &at Lhe ions are tctra~onally distorted in rhcse exited
staIcs. The dcpolarisation ratio of ~hc tr2 band of [TcBr,l- at rcsonancc with the TIru .- A,r r&tion is fwnd to be 0.1s.
in close agreement with that expected (3/M) for :he first ovtnone of a doubly degenerate vi br ar i or . cciupled to P trip&
1. Introduction
The A-term model for resonance Raman
scattering (RRS) is satisfactory only if the elec-
tronic energy is weakly dependent on the nuclear
coordinates. When vibronic coupling is strong. as
is common for vibrating molecules in degenerate
states where Jahn-Teller (JT) coupling and Ren-
ner-Telier (RT) coupling may occur. alternative
theoretical models are required. The ones which
have been described span a wide range of coupling
strengths and cover all possible combinations of
vibrational and dectronic degeneracy. Only a few
RR experiments have, however, been carried out
on molecules which exhibit strong vibronic cou-
pling. In one such experiment involving the
[TeBr,]- ion [l]. it was observed that. at reso-
nance with the lowest electronic band, the band
assi gned t o t he v2(c +,) stretching vibration was
more ezlxtnced than that assigned to the ul(a,,)
stretching vibration. Such a result could not be
satisfactorily explained using the A- and B-term
models of RR!% In the hope of revealing the RRS
behaviour of such strongly coupled systems, it was
decided to undertake a detailed study of the
hexahalotelhuate(IV) ions, both in the ultraviolet
as well as in the visible regions of the spectrum.
Several Ratnan spectroscopic studies have been
carried out on various salts of the [TeX,]- ions
under a variety of experimental conditions [?-91.
Most workers observed three bands in the spectra
of both the chloride and bromide ions anti as-
signed them to the w,(a,s), vz(er) and vs(t2s)
fundamentals of the ions_ The intensities of the u2
and ps bands show preresonance enhancement [5].
Recent work on the temperature dependence of
the intensities of the low-wavenumber bands by
Berg has led to the assignment of a numbor of
lattice vibrations [6.7]_
The electronic structures of these ions have
been examined using visible and ultraviolet ab-
sorption [5,10,11] and emission spectroscopy [12]_
The reported absorption spectra are all identical.
In all cases the assignment of the lowest wavenum-
ber absorption band (called the A band) in the
spectra of the chloride and bromide was to a
spin-forbidden 3T,U t IA,, transition_ The next
absorption band (called the B band) was assigned
by Stuflcens [5] to a E, or 3T& -Ats transition;
Couch et al. [ll] prefer- however. to assign it to
another spin-orbit component of the l& - Ars
transition_ The absorption band occurring at thr=
highest observed wavenumber was assigned to a
tT,u - A,,
transition in both reports [S.ll], and
called the C band_
The splitting of theAandCbandshasbeen
0301-0104/&t/$03.00 6 Elsevier Science Publishers B.V.
(North-Holland Physics Publishing Division)
attributed by Couch et aL ill] to a lowering of the
symmetry of the ion in its excited state, is_ to
static Mm-Teller effects_ Stufkens cites work
[13.&t] in support of his proposal that the ob-
served temperature dependence of the splitting is
due to dynamic Jahn-Teller effects In particular
Chos work [l?] suggests that the shape of the C
band can only be explained if the electronic and
Gbrational uavefunctions are strongly coupled via
a t,, vibtation.
Irradiation of [SeX,]- and r;reX6]- ions with
ultraviolet lig$lE yields strong emission spectm [12)-
For thr selenium compltxa well-resolved vibra-
tional fine structure is observed on the emission
bands. the spacing between the components being
240 and 154 cm- for the chloride and bromide.
respectively The progression-forming modes were
assigried to es Fundamentals: these occur in the
ground elestronic states at 242 and I50 cm- for
the chloride and bromide. respectively_ The emis-
sion spectra of the [Sex,]- ions were cakuiated
using a model which involves the vibronic cou-
pling of a triply degenerate electronic state (T)
with a doubly degenerate vibrational state (e). with
inclusion of the effects of spin-orbit coupling A
potential energy surface for the emitting (3Tr,)
excited state was calculated for a range of model
parameters_ The ion u-as shown to change from 0,
symmetry in its ground state to Dar, symmetry in
its excited state. the bonds along the : axis in the
excited state being 02 A longer than those in the
_eround state.
Longuet-Higgins [15] has shown that, for a dou-
biy degenerate vibration (e) involved in the *T
coupling of a doubiy degenerate electronic state
<E>_ is E x e -plins the distorted excited state
can k dacribed by a pair of harmonic potential-
energy surfaces displaced and depressed from the
uncoupkd surface which represents the undis-
torted excited staie. The selection rules for elec-
tronic transitions to and from excited states tmder-
going IT distortion are relaxed_ and overtone pro-
gressions of coupling modes in the excited state
are sometimes observed in the eiatronic spectrum-
tcrlore recently Tsuboi et al. [la] have calculated
the displacement of the excited-state potential
surface relative to that of the ground state for the
Tz + A, electronic transition of the chromate(W)
ion_ Using a similar model to that of Longuet-Iiig-
gins. they succeeded in fitting the experimental
excitation profile of the band assigned to the vs(tz)
vibrationat mode to a t k or et i c af one whose shape
was determined by the displacement of the ex-
cited-state potential energy surface_
The enhancements of bands assigned to non-
totally symmetric modes in metalloporphyrins
f17.131 have also been attributed to .IT coupling
within a doubly degenerate excited state_ The theo-
retically and experimentally determined excitation
profiles of these bands were found to be in good
agreement with one another [17]_
The relationship between lT coupling and RRS
has also been formulated using diabatic potentials
[I9]_ This formulation allou-s an examination of
vibronic coupling over a complete range of cou-
pling strengths_ For strong (JT) coupling this ap-
proach leads to results similar to that of Longuet-
Higgins. The inclusion of non-linear coupling terms
leads to the prediction of polarisation dispersion
for the overtones of certain fundamentals [2021].
3; Experimental
Raman spectra were recorded on Spex 1401
and 14015 spectrometers, in conjunction with
Coherent Radiation model CRIZLJV and 3000 K
lasers. Samples were spun at = 1500 rev min- in
order to avoid thermal degradation-
4, Results and d&cm&on
It was decided to investigate the RRS behaviour
of the tetrabutyIammonium salts of the veX,]-
ions (where X = Cl or Br), because these salts are
readily soIuble in organic solvents By making
measurements on solutions, solid-state effects such
as site symmetry splitting etc., can be ruled out
from the begkning. This procedure has the disad-
vantage. however, that bands dose to the exciting
line are often obscured by a rather broad Rayleig!r
wing, and for this reason excitation profile mea-
surements could not be made for the Do &nds of
these ions.
!Mutions of the complexes were prepared by
distilling methyl cyanide off dry phosphorus(V)
oxide into g&s cells containing the complexes.
The solutions were then frozen and the cells
evacuated and sealed.
i s. I. El ectroni c specrra
The complexes were dissolved in dry methyl
cyanide as described above. and their electronic
spectra were recorded_ The results, which were
found to be identical with those previously re-
ported 15.91, are summarised in table 1.
4.2 Resomznce Raman spectra and exci tati on
profi l es
The Raman spectra of the complexes were re-
corded for exciting radiation in the range
15 000-30000 cm-_ Intensity measurements were
made relative to the 918 cm- Raman band of
methyl cyanide and were corrected for instrumen-
tal response_ Electronic spectra of the sampks
were recorded both before and after irradiation so
that any decomposition of the complexes might be
detected. In the case of the chloride a slight reduc-
tion in the intensities of all bands in the electronic
absorption spectrum was observed. indicating that
the complex had slightly decomposed.
Table 1
Assign-t and wawmm&as of rhe bands obscmcd in the
ekctronic absorption spectra of [(n-C,H,),N],TeX,]. fm
X = Cl or Br. as methyl cyanide solutions at 295 K
Wamumbcr (cm-)
x=Cl X==Br
Asigxlmalt
24700 21300
2ssao 22400
L .- A,,
31ooo 26700 T,u - J%E
33000 28400
34700 3oooo l-r,. - A
1s
38200 31200
Fig. 1. Electronic absorption spcccrum of the comptex [(n-
C,H,),N],fTcCt,] as a methyl cyanide solution. rogether with
excitation profdcs of the vi and V~ bands of :he anion Raman
inknitia xv- tnwsurcd relative to the 9i8 cm- band of
methyl cyanide.
The excitation profiles of the Y* and v1 bands of
[TeCl,]- and [TeBr6]- are shown plotted, to-
gether with their electronic absorption spectra, in
figs_ 1 and 2 respectively_ The excitation prcfrle of
v1 is slightly enhanced =2OOOcm-totheredof
the electronic band attributed to the 3TrU +-*A,,
transition, is at a minimum in the vicinity of this
Fig 2_ Elccfronic absorption spccmm of the amlpll [(n-
C.H,),wJfeBr,] as a mc!hyl cyanide solution. together with
&e excitation p&ides of ttie w, and wz bands of the anion
Raman intem&ies u-err meanved rdative to the 918 cm-
band of me&y1 qtidc.
electronic band maximum and then reaches a
second ma..imum a Iittie to the low wavenumber
side of the electronic band attributed to the TtU
+--!A,, transition_ That of V? for each ion_ on the
other hand, closely follows the eontour of the
Tru -k,, band before rising again once the ex-
citing line falls within the contour of the TIy -
A,= band_
Since it is the band assigned to the V= vibration
which is most enhanced_ it folIous that it is this
mode which is most effective in converting the
molecule from its ground to its excited state con-
figuration [22]_ The effect of the vz(es) vibration is
to convert the [TeX,]- ion from 0, to Du,
symmctq-_ and hence one predicts that the ion has
D, symmetry in the T, excited state i-e_ that it
is tttragonall? distorted_ This conclusion is in
agreement with that deduc- for the ZUI~O~OUS
[!kX,]- ions from their emission spectra. The
decrease in the inter&t\; of the or band of both
ions in the region of the sTu, + k,, transition is
attributed to mterference between the contribu-
tions to the transition polarisability from the 3T,y
and T, excited states (23-X]_
Excitation within the contour of the band as-
signed tc the allowed TtU + tAlr transition of the
[TeCI,]- was noz possible be&&e it lies beyond
i
Table 2
.Assignmas. u;l\mumbcrs_ peak &~&KS and fu-hm of the
hands observed in the resonance Ranun spcctn of [(R-
C,H,),N12[ TeX,] f or X = Cl or Br
\V~\Wl l l t l l k r fwhm RPH -
(Em-) (Cm_)
X=a
2s; IS 100
241 20 71
x = BrC
167 11 100
I4S 15 41
74 15 15
2% 20 25
312 IS
231 12
-t-w 30 7
= RPH denotes ~&&LX pztk hei@_
Exziting uirh 337.5 nm radiation.
CD Exciting with 356.4 run radiation.
the exciting line of highest available wavenumber.
The RR spectrum obtained when exciting with
3375 nm radiation (fig 3a) shows some enhance-
ment of both the =I and Ye bands_ The analogous
transition in the electronic absorption spectrum of
the [TeBr,]- lies at lower wavenumber- and in
this case resonance could be achieved using the
available exciting lines_ Irradiating with 356-4 nm
radiation yields a spectrum containing two over-
tone progressions. one in V~ as far as 3vz and the
other in P, as far as 2v, (fig 3b)_ Some enhance-
ment of the vs band was also observed_ The RR
spectroscopic resuhs are summarised in table 2
The great enhancement of the v2 band suggests
that the [TeBr,]- ion undergoes a considerable
tetEi gOKId distortion in its T,, excited state.
4-3. Depol ari sati on rati os
Depohuisation ratio measurements were also
made using the full range of available exciting
lines. The depolarisation ratios of the bands as-
signed to the fundamentals Y, and vs of the
.[TeBr,]- ion were found to be 0.00 + 0.02 and
O-75 f O_lO_ respectively_ and showed_ as expected
[21]. no dispersion_ For the [Tecl,] ion. the de-
polarisation ratios of the P, and pz bands were
found to be 0.00 + O-02 and 0.75 + 0.05. respec-
tively. and again showed no dispersion. The de-
polarisation ratio of the uz band of the [TeBr,]-
ion. however. was found to be 1.00 f 0.10 in the
region of the 3TtU * tA,s transition and 0.75 + 0.05
in all other regions. The reason for this observa-
tion is not clear_ It has been shown that, in the
scattering tensor for an er vibration of a molecule
with 0, symmetry, all the off-diagonal elements
are zero [26]. Consequently there can be no contri-
bution to the antisymmetric tensor invariant. and
so the depolarisation ratio should be O-75.. irre-
spective of the wavenumber of the exciting line.
Coordination of the solvent may be ruled out
because similar experiments using dichloro-
methane as solvent rather than methy cyanide
yielded the same result.
Zgierski and Pawlikowski have shown that, for
linear vibronic coupling. the band assigned to a
first overtone of a doubly degenerate vibration
coupled to a triply degenerate electronic state,
should show no dispersion of its polarisation [21]
and that its depolarisation ratio may be under-
stood as follows: the first overtone of an es mode
may obtain intensity via two channels. because
E, x E, 3 A,, + A, f Es (As is not Raman ac-
tive in the 0, point group)_ The ratio of the
intensities produced by each channel is fiied for
linear vibronic coupling and lies between 0.00
(pure A,,) and 0.75 (pure E,), the actual ratio
being determined by symmetry. Measure ments of
the depolarisation ratio of the band assigned to
25 when exciting with 28057 cm- radiation gave
a p value of O-18 f 0.02 in good agreement with
the predicted value (0.21). It should be noted.
however. that the 2~~ and 2q bands overlap and
hence that this result is based only on measure-
ments of relative peak heights
5. coneIusions
The experimental results are generally in good
agreement with the predictions of Zgierski and
Pawlikowski 1211. for the resonance Raman
scattering by strongly coupled T x e systems Their
model adequately accounts for the depolarisation
ratios of the yzV 29, and vs bands of the [TeBr,J-
ion but not for that of the v, band in the region of
the spin forbidden 3TrU + A,, transition_
The observation of an overtone progression in
the band assigned to the v~(s) vibration &>f the
[TeBr,J- ion when exciting within the contour of
its TrU -Alb transition, is taken as evidence in
favour of a tetragonally distorted geometry for the
ion in this excited state, similar to that prcposed
for [SeBr,]- and (!&Cl,]- [12]. These onclu-
sions are in contrast to the prediction by Ct.0 1131
that coupling via the t,, mode ought to be the
more important_ If this were the case then an
overtone progression in the ps mode woulc! have
been expected.
Acknowledgement
The authors thank the SERC for financial sup-
port and Dr. T-l_ Dines for useful comments.
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