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

R. Biswas; J. E. Lewis; M. Maroncelli

doi:10.1016/S0009-2614(99)00838-6

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

R. Biswas, J. E. Lewis, M. Maroncelli

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Abstract

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≤ρ/ρ_c≤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 CO₂ and CHF₃, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C₂H₆.

Original language	English (US)
Pages (from-to)	485-494
Number of pages	10
Journal	Chemical Physics Letters
Volume	310
Issue number	5-6
DOIs	https://doi.org/10.1016/S0009-2614(99)00838-6
State	Published - Sep 10 1999

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1016/S0009-2614(99)00838-6

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@article{f3fbfc070d8b4082bd5ffc95cec1beba,

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

abstract = "Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (Tc=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≤ρ/ρc≤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 CO2 and CHF3, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C2H6.",

author = "R. Biswas and Lewis, {J. E.} and M. Maroncelli",

note = "Funding Information: The authors would like to thank Kenji Takahashi and Charles Jonah for sharing the results of their studies prior to publication, as well as helpful discussions on the analysis methods they employed, and also to Abby Robinson for her contributions to the initial stages of this work. Partial support of this research by the US Office of Naval Research is also gratefully acknowledged.",

year = "1999",

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doi = "10.1016/S0009-2614(99)00838-6",

language = "English (US)",

volume = "310",

pages = "485--494",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

number = "5-6",

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TY - JOUR

T1 - Electronic spectral shifts, reorganization energies, and local density augmentation of Coumarin 153 in supercritical solvents

AU - Biswas, R.

AU - Lewis, J. E.

AU - Maroncelli, M.

N1 - Funding Information: The authors would like to thank Kenji Takahashi and Charles Jonah for sharing the results of their studies prior to publication, as well as helpful discussions on the analysis methods they employed, and also to Abby Robinson for her contributions to the initial stages of this work. Partial support of this research by the US Office of Naval Research is also gratefully acknowledged.

PY - 1999/9/10

Y1 - 1999/9/10

N2 - Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (Tc=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≤ρ/ρc≤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 CO2 and CHF3, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C2H6.

AB - Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (Tc=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≤ρ/ρc≤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 CO2 and CHF3, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C2H6.

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U2 - 10.1016/S0009-2614(99)00838-6

DO - 10.1016/S0009-2614(99)00838-6

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SN - 0009-2614

VL - 310

SP - 485

EP - 494

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 5-6

ER -

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

Abstract

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