Electronic spectral shifts, reorganization energies, and local density augmentation of Coumarin 153 in supercritical solvents

被引:80
作者
Biswas, R [1 ]
Lewis, JE [1 ]
Maroncelli, M [1 ]
机构
[1] Penn State Univ, Dept Chem, University Pk, PA 16802 USA
关键词
D O I
10.1016/S0009-2614(99)00838-6
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (T-c = 5 K) are measured using fluorescence spectroscopy. Reorganization energies are 320 +/- 70 and 770 +/- 70 cm(-1) in CO2 and CHF3, respectively - nearly independent of density (0.3 less than or equal to rho/rho(c) less than or equal to 2.1). The spectral shifts imply similar effective local densities in all three solvents. These effective densities can exceed 3-5 times the bulk density. In CO, and CHF,, the maximum density augmentation calculated from emission shifts is similar to 20% greater than that calculated from excitation shifts. No such difference is found in C2H6. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:485 / 494
页数:10
相关论文
共 20 条
[1]   REFRACTIVE INDEXES OF ETHANE, CARBON-DIOXIDE, AND ISOBUTANE [J].
BESSERER, GJ ;
ROBINSON, DB .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1973, 18 (02) :137-140
[2]   SPECTROSCOPIC DETERMINATION OF SOLUTE FLUID CLUSTER SIZE IN SUPERCRITICAL N2O [J].
BETTS, TA ;
ZAGROBELNY, J ;
BRIGHT, FV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (21) :8163-8171
[3]   ISOCHORIC (P, VM, T) MEASUREMENTS ON CO2 AND ON (0.982CO2+0.018N2) FROM 250-K TO 330-K AT PRESSURES TO 35 MPA [J].
ELY, JF ;
HAYNES, WM ;
BAIN, BC .
JOURNAL OF CHEMICAL THERMODYNAMICS, 1989, 21 (08) :879-894
[4]   THE ELECTRONIC ORIGIN OF THE PIPISTAR ABSORPTION OF AMINO COUMARINS STUDIED IN A SUPERSONICALLY COOLED FREE JET [J].
ERNSTING, NP ;
ASIMOV, M ;
SCHAFER, FP .
CHEMICAL PHYSICS LETTERS, 1982, 91 (03) :231-235
[5]   ESTIMATING THE TIME-ZERO SPECTRUM IN TIME-RESOLVED EMISSION MEASUREMENTS OF SOLVATION DYNAMICS [J].
FEE, RS ;
MARONCELLI, M .
CHEMICAL PHYSICS, 1994, 183 (2-3) :235-247
[6]   SUBPICOSECOND MEASUREMENTS OF POLAR SOLVATION DYNAMICS - COUMARIN-153 REVISITED [J].
HORNG, ML ;
GARDECKI, JA ;
PAPAZYAN, A ;
MARONCELLI, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (48) :17311-17337
[7]   CHARGE-TRANSFER-STATE FORMATION IN SUPERCRITICAL FLUID - (N,N-DIMETHYLAMINO)BENZONITRILE IN CF3H [J].
KAJIMOTO, O ;
FUTAKAMI, M ;
KOBAYASHI, T ;
YAMASAKI, K .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (05) :1347-1352
[8]  
Lewis J. M., UNPUB
[9]   Supercritical fluids: Introduction [J].
Noyori, R .
CHEMICAL REVIEWS, 1999, 99 (02) :353-354
[10]  
PATEL N, UNPUB