Paramagnetic resonance of polycrystalline VCl4 diluted with TiCl4 has been observed near 9,24, and 36 GHz below 9°K. Both g values and hyperfine A tensors are axially symmetric and temperature independent with the same principal axes: g‖ = 1.920, g⊥ = 1.899, | A‖ | = 72 G, | A⊥ | = 120 G⁠. The average g value obtained from susceptibility data is in agreement with the resonance value. The paramagnetic relaxation time T1 varies with temperature as shown by the relation T1 = 2 × 10− 9exp(25/T) sec, indicating the presence of a potential barrier approximately 18 cm− 1 in height. The results indicate a static Jahn–Teller distortion, but with large zero‐point vibrations. This situation is in between Ballhausen–de Heer's ligand field and Ball‐hausen–Liehr's crystal‐field calculations.

Topics
Jahn-Teller distortion, Ligand fields, Crystal field theory, Polycrystalline material, Hyperfine structure, Chemical compounds, Potential energy barrier
1.
W.
Klemm
 and
E.
Hoschek
,
Z. Anorg. Allgem. Chem.
226
,
359
(
1936
).
Google Scholar
Crossref
Search ADS
 
2.
A. G.
Whittaker
 and
D. M.
Yost
,
J. Chem. Phys.
17
,
188
(
1949
).
Google Scholar
Crossref
Search ADS
 
3.
R. J. H. Clark and D. J. Machin, J. Chem. Soc. 1963, 4430.
4.
F. A.
Blankenship
 and
R. L.
Belford
,
J. Chem. Phys.
36
,
633
(
1962
).
Google Scholar
Crossref
Search ADS
 
5.
M. F. A.
Dove
,
J. A.
Creighton
, and
L. A.
Woodward
,
Spectrochim. Acta
18
,
267
(
1962
).
Google Scholar
Crossref
Search ADS
 
6.
F.
Pennella
 and
W. J.
Taylor
,
J. Mol. Spectry.
11
,
321
(
1963
).
Google Scholar
Crossref
Search ADS
 
7.
Y.
Morino
 and
H.
Uehara
,
J. Chem. Phys.
45
,
4543
(
1966
).
Google Scholar
Crossref
Search ADS
 
8.
J. C. W.
Chien
 and
C. R.
Boss
,
J. Am. Chem. Soc.
83
,
3767
(
1961
).
Google Scholar
Crossref
Search ADS
 
9.
F. G.
Herring
,
C. A.
McDowell
, and
H.
Nakajima
,
Colloq. Intern. Centre Natl. Rech. Sci. (Paris)
164
,
395
(
1966
).
Google Scholar
 
10.
D. W. Pratt, Lawrence Radiation Laboratory Report UCRL‐17406, University of California, Berkeley, California, 1967.
11.
C. J.
Ballhausen
 and
A. D.
Liehr
,
Acta Chem. Scand.
15
,
775
(
1961
).
Google Scholar
Crossref
Search ADS
 
12.
C. J.
Ballhausen
 and
J.
de Heer
,
J. Chem. Phys.
43
,
4304
(
1965
).
Google Scholar
Crossref
Search ADS
 
13.
L. L.
Lohr
, Jr., and
W. N.
Lipscomb
,
Inorg. Chem.
2
,
911
(
1963
).
Google Scholar
Crossref
Search ADS
 
14.
G. A.
Candela
 and
R. E.
Mundy
,
IRE Trans. Instr.
I‐11
,
106
(
1962
).
Google Scholar
 
15.
J. S. Griffith, The Theory of Transition Metal Ions (Cambridge University Press, London, 1961), pp. 280, 284, and 437.
16.
R. N.
Rogers
 and
G. E.
Pake
,
J. Chem. Phys.
33
,
1107
(
1960
).
Google Scholar
Crossref
Search ADS
 
17.
A. Abragam, The Principles of Nuclear Magnetism (Oxford University Press, London, 1961), pp. 206 and 315.
18.
B. W.
Mangum
 and
R. P.
Hudson
,
J. Chem. Phys.
44
,
704
(
1966
).
Google Scholar
Crossref
Search ADS
 
19.
See review by C. J. Ballhausen, Introduction to Ligand Field Theory (McGraw‐Hill Book Co., New York, 1962), p. 270; V++(d1) and Cu2+(d9) have spin‐orbit coupling constants £ of opposite signs.
20.
B.
Bleaney
,
K. D.
Bowers
, and
R. S.
Trenam
,
Proc. Roy. Soc. (London)
A228
,
157
(
1955
).
Google Scholar
 
21.
D. E.
O’Reilly
 and
T.
Tsang
,
J. Chem. Phys.
46
,
1291
(
1967
).
Google Scholar
Crossref
Search ADS
 
22.
C. B. P.
 
Finn
,
R.
 
Orbach
, and
W. P.
 
Wolf
,
Proc. Phys. Soc. (London)
 
77
,
261
(
1961
);
Google Scholar
Crossref
Search ADS
 
R.
Orbach
,
Proc. Roy. Soc. (London)
A264
,
458
(
1961
).
Google Scholar
 
23.
H. J.
Berthold
,
Angew. Chem.
76
,
575
(
1964
).
Google Scholar
Crossref
Search ADS
 
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1968
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