Vibrational lifetimes and absorption spectra of the asymmetric CO stretching mode (∼1990 cm−1) of W(CO)6 in supercritical CO2 are reported as functions of solvent density and temperature. Close to the critical temperature, the observables are density independent over a twofold range of density. Possible explanations are discussed for this unique behavior.

1.
J. B.
Hannay
and
J.
Hogarth
,
Proc. R. Soc. London
29
,
324
(
1879
);
J. B.
Hannay
,
Proc. R. Soc. London
30
,
484
(
1880
).,
Proc. R. Soc. London
2.
C. A.
Eckert
,
D. H.
Ziger
,
K. P.
Johnston
, and
T. K.
Ellison
,
Fluid Phase Equilib.
14
,
167
(
1983
);
C. A.
Eckert
,
D. H.
Ziger
,
K. P.
Johnston
, and
S.
Kim
,
J. Phys. Chem.
90
,
2738
(
1986
).
3.
P. G.
Debenedetti
,
Chem. Eng. Sci.
42
,
2203
(
1987
).
4.
H. D.
Cochran
,
L. L.
Lee
, and
D. M.
Pfund
,
Fluid Phase Equilib.
34
,
219
(
1987
);
M.
Pfund
,
L. L.
Lee
, and
H. D.
Cochran
,
Fluid Phase Equilib.
39
,
161
(
1988
).,
Fluid Phase Equilib.
5.
J. G.
Kirkwood
and
F. P.
Buff
,
J. Chem. Phys.
19
,
774
(
1951
).
6.
I. B.
Petsche
and
P. G.
Debenedetti
,
J. Chem. Phys.
91
,
7075
(
1989
).
7.
J-L. M.
Abboud
,
G.
Guiheneuf
,
M.
Essfar
,
R. W.
Taft
, and
M. J.
Kamlet
,
J. Phys. Chem.
88
,
4414
(
1984
).
8.
N. S.
Bayliss
and
E. G.
McRae
,
J. Phys. Chem.
58
,
1002
(
1954
);
E. G.
McRae
,
J. Phys. Chem.
61
,
562
(
1957
).,
J. Phys. Chem.
9.
L.
Onsager
,
J. Am. Chem. Soc.
58
,
1486
(
1936
).
10.
T. W.
Zerda
,
B.
Wiegand
, and
J.
Jonas
,
J. Chem. Eng. Data
31
,
274
(
1986
).
11.
J. P.
Blitz
,
C. R.
Yonker
, and
R. D.
Smith
,
J. Phys. Chem.
93
,
6661
(
1989
).
12.
G. E.
Bennett
and
K. P.
Johnston
,
J. Phys. Chem.
98
,
441
(
1994
).
13.
Y-P.
Sun
,
G.
Bennett
,
K. P.
Johnston
, and
M. A.
Fox
,
J. Phys. Chem.
96
,
10001
(
1992
).
14.
R. D.
Schulte
and
J. F.
Kauffman
,
Appl. Spectrosc.
49
,
31
(
1995
).
15.
M.
Lee
,
G. R.
Holtom
, and
R. M.
Hochstrasser
,
Chem. Phys. Lett.
118
,
359
(
1985
).
16.
A.
Tokamakoff
,
B.
Sauter
, and
M. D.
Fayer
,
J. Chem. Phys.
100
,
9035
(
1994
).
17.
P.
Moore
,
A.
Tokmakoff
,
T.
Keyes
, and
M. D.
Fayer
,
J. Chem. Phys.
103
,
3325
(
1995
).
18.
V. M.
Kenkre
,
A.
Tokmakoff
, and
M. D.
Fayer
,
J. Chem. Phys.
101
,
10618
(
1994
).
19.
A.
Tokmakoff
,
C. D.
Marshall
, and
M. D.
Fayer
,
JOSA B
10
,
1785
(
1993
).
20.
J. F.
Ely
,
W. M.
Haynes
, and
B. C.
Bain
,
J. Chem. Thermodynamics
21
,
879
(
1989
).
21.
D. W.
Oxtoby
,
Adv. Chem. Phys.
47
,
487
(
1981
).
22.
A. M.
Benson
,Jr.
and
H. G.
Drickamer
,
J. Chem. Phys.
27
,
1164
(
1957
);
R. R.
Wiederkehr
and
H. G.
Drickamer
,
J. Chem. Phys.
28
,
311
(
1958
); ,
J. Chem. Phys.
T. G.
Politis
and
H. G.
Drickamer
,
J. Chem. Phys.
74
,
263
(
1981
).,
J. Chem. Phys.
23.
M. A. Anisimov, Critical Phenomena in Liquids and Liquid Crystals (Gordon and Breach, Philadelphia, 1991).
24.
R. S. Urdahl, K. D. Rector, D. J. Myers, P. H. Davis, and M. D. Fayer (in preparation).
This content is only available via PDF.
You do not currently have access to this content.