T 1 Relaxation of Perylene in Fluid Ethane: Pressure-Dependent Changes in Short-Range Organization

Abstract

We report our measurements of vibrational population relaxation of the v₇ (1375 cm⁻¹) mode of perylene in ethane at a series of fluid pressures. The data show that T₁ decreases with increasing fluid pressure and that the dependence of T₁ on pressure is not consistent with predictions based on simple spatial or stoichiometric considerations. The data indicate a nonrandom orientational distribution of the solvent molecules about the solute where the portion of the solvent environment sensed by the perylene v₁ coordinate changes from one ordered state to another ordered state with increasing pressure.

Keywords

Vibrational population relaxation Supercritical fluids Organization in fluids

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References

Fleming

G. R.

, Chemical Applications of Ultrafast Spectroscopy (Oxford University Press, Oxford, 1986), and references therein.

Debye

, Polar Molecules (Chemical Catalog Company, New York, 1929), p. 84.

Perrin

, J. Phys. Radium 5, 497 (1934).

C.-M.

and Zwanzig

, J. Chem. Phys. 60, 4354 (1974).

Youngren

G. K.

and Acrivos

, J. Chem. Phys. 63, 3846 (1975).

Edward

J. T.

, J. Chem. Educ. 47, 261 (1970).

Porter

Sadkowski

P. J.

and Tredwell

C. J

, Chem. Phys. Lett. 49, 416 (1977).

Spears

K. G.

and Cramer

L. E

, Chem. Phys. 30, 1 (1978).

Millar

D. P.

Shah

and Zewail

A. H

, Chem. Phys. Lett. 66, 435 (1979).

10.

Waldeck

D. H.

Cross

A. J.

Jr. McDonald

D. B.

and Fleming

G. R

, J. Chem. Phys. 74, 3381 (1981).

11.

von Jena

and Lessing

H. E

, Chem. Phys. Lett. 78, 187 (1981).

12.

Spears

K. G.

and Steinmetz

K. M

, J. Phys. Chem. 89, 3623 (1985).

13.

Gudgin-Templeton

E. F.

Quitevis

E. L.

and Kenney-Wallace

G. A

, J. Phys. Chem. 89, 3238 (1985).

14.

Justus

B. L.

Cox

A. J.

Butz

K. W.

and Scott

G. W

, Chem. Phys. 119, 125 (1988).

15.

Blanchard

G. J.

, J. Phys. Chem. 93, 4315 (1989).

16.

Quitevis

E. L.

and Horng

M.-L

, J. Phys. Chem. 94, 5684 (1990).

17.

Dutt

G. B.

Doriswamy

Periasamy

and Venkataraman

, J. Chem. Phys. 93, 8498 (1990).

18.

Blanchard

G. J.

, J. Phys. Chem. 95, 5293 (1991).

19.

Alavi

D. S.

and Waldeck

D. H

, J. Phys. Chem. 95, 4848 (1991).

20.

Vauthey

, Chem. Phys. Lett. 216, 530 (1993).

21.

Blanchard

G. J.

and Cihal

C. A

, J. Phys. Chem. 92, 5950 (1988).

22.

Blanchard

G. J.

, J. Phys. Chem. 92, 6303 (1988).

23.

Blanchard

G. J.

, Anal. Chem. 61, 2394 (1989).

24.

Beddard

G. S.

Doust

and Hudales

, Nature 294, 145 (1981).

25.

Christensen

R. L.

Drake

R. C.

and Phillips

, J. Phys. Chem. 90, 5960 (1986).

26.

Gudgin-Templeton

E. F.

and Kenney-Wallace

G. A

, J. Phys. Chem. 90, 2896 (1986).

27.

Gudgin-Templeton

E. F.

and Kenney-Wallace

G. A

, J. Phys. Chem. 90, 5441 (1986).

28.

Dutt

G. B.

and Doriswamy

, J. Chem. Phys. 96, 2475 (1992).

29.

Mokhtari

Chesnoy

and Laubereau

, Chem. Phys. Lett. 155, 593 (1988).

30.

Wagener

and Richert

, Chem. Phys. Lett. 176, 329 (1991).

31.

Declemy

Rulliere

and Kottis

, Chem. Phys. Lett. 133, 448 (1987).

32.

Castner

E. W.

Maroncelli

and Fleming

G. R

, J. Chem. Phys. 86, 1090 (1987).

33.

Nagarajan

Brearly

A. M.

Kang

T. J.

and Barbara

P. F

, J. Chem. Phys. 86, 3183 (1987).

34.

Maroncelli

and Fleming

G. R

, J. Chem. Phys. 86, 6221 (1987).

35.

Simon

J. D.

, Acc. Chem. Res. 21, 128 (1988).

36.

Barbara

P. F.

and Jarzeba

, Adv. Photochem 15, 1 (1990).

37.

Maroncelli

Fee

R. S.

Chapman

C. F.

and Fleming

G. R

, J. Phys. Chem. 95, 1012 (1991).

38.

Jarzeba

Walker

G. C.

Johnson

A. E.

and Barbara

P. F

, Chem. Phys. 152, 57 (1991).

39.

Agmon

, J. Phys. Chem. 94, 2959 (1990).

40.

McCarthy

P. K.

and Blanchard

G. J

, J. Phys. Chem. 97, 12505 (1993).

41.

Jiang

McCarthy

P. K.

and Blanchard

G. J

, Chem. Phys. 183, 249 (1994).

42.

Landanyi

B. M.

and Levinger

N. E

, J. Chem. Phys. 81, 2620 (1984).

43.

Hambir

S. A.

Jiang

and Blanchard

G. J

, J. Chem. Phys. 98, 6075 (1993).

44.

Jiang

and Blanchard

G. J

, J. Phys. Chem. 98, 9411 (1994).

45.

Jiang

and Blanchard

G. J

, J. Phys. Chem. 98, 9417 (1994).

46.

Jiang

and Blanchard

G. J

, J. Phys. Chem. 99, 7904 (1995).

47.

Jiang

and Blanchard

G. J

, J. Phys. Chem. 98, 6436 (1994).

48.

Supercritical Fluid Science and Technology, ACS Symposium Series 406, Johnston

K. P.

and Penninger

J. M. L

, Eds. (American Chemical Society, Washington, D.C., 1989).

49.

Supercritical Fluid Technology: Theoretical and Applied Approaches in Analytical Chemistry, ACS Symposium Series 488, Bright

F. V.

and McNally

M. E. P

, Eds. (American Chemical Society, Washington, D.C., 1992).

50.

Supercritical Fluid Technology: Reviews in Modern Theory and Applications, Bruno

T. J.

and Ely

J. F

, Eds. (CRC Press, Boca Raton, Florida, 1991).

51.

Supercritical Fluid Engineering Science: Fundamentals and Applications, ACS Symposium Series 514, Kiran

and Brennecke

J. F

, Eds.: (American Chemical Society, Washington, D.C., 1993).

52.

McHugh

M. A.

and Krukonis

V. J

, Supercritical Fluid Extraction: Principles and Practice (Butterworths, Boston, 1993).

53.

Rhodes

T. A.

O'Shea

Bennett

Johnston

K. P.

and Fox

M. A

, J. Phys. Chem. 99, 9903 (1995).

54.

Zhang

Lee

L. L.

and Brennecke

J. F

, J. Phys. Chem. 99, 9268 (1995).

55.

Eckert

C. A.

Ziger

D. H.

Johnston

K. P.

and Ellison

T. K

, Fluid Phase Equil 14, 167 (1983).

56.

Betts

T. A.

, J. Zagrobelny, and F. V. Bright, J. Am. Chem. Soc. 114, 8163 (1992).

57.

Betts

T. A.

and Bright

F. V

, Appl. Spectrosc. 44, 1196 (1990).

58.

Jiang

Hambir

S. A.

and Blanchard

G. J

, Opt. Commun. 99, 216 (1993).

59.

Bado

Wilson

S. B.

and Wilson

K. R

, Rev. Sci. Instrum. 53, 706 (1982).

60.

Andor

Lorincz

Siemion

Smith

D. D.

and Rice

S. A

, Rev. Sci. Instrum. 55, 64 (1984).

61.

Blanchard

G. J.

and Wirth

M. J

, Anal. Chem. 58, 532 (1986).

62.

Gray

C. G.

and Gubbins

K. E

, Theory of Molecular Fluids, Vol. 1, Fundamentals (Oxford Science, Oxford, 1984), pp. 91–100.

63.

Younglove

B. A.

and Ely

J. F

, J. Phys. Chem. Ref. Data 16, 577 (1987).

64.

Bauer

D. R.

Braumann

and Pecora

, J. Am. Chem. Soc. 96, 6840 (1974).

65.

Förster

, Z. Naturforsch A4, 321 (1949).

66.

Förster

, Faraday Disc. Chem. Soc. 27, 7 (1959).

67.

Rigby

Smith

E. B.

Wakeham

W. A.

and Maitland

G. C

, The Forces Between Molecules (Oxford Science, 1986), p. 7.

68.

Zerda

T. W.

Song

Oxford and Jonas

, Appl. Spectrosc. 40, 1194 (1986).

69.

Blanchard

G. J.

and Wirth

M. J

, J. Phys. Chem. 90, 2521 (1986).

70.

Blanchard

G. J.

, J. Chem. Phys. 87, 6802 (1987).