Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents
Abstract
Solvent-induced shift of optical transition lines is traditionally described by the Lippert–McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. We have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived, and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for the reaction field of permanent dipoles in the Lippert–McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert–McRae equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, nonadditive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Lastly, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert–McRae formula.
- Publication Date:
- Research Org.:
- Arizona State Univ., Tempe, AZ (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1345838
- Alternate Identifier(s):
- OSTI ID: 1347381
- Report Number(s):
- BNL-113670-2017-JA
Journal ID: ISSN 1089-5639
- Grant/Contract Number:
- SC0015641; SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 11; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electron transfer; solvent-induced shift
Citation Formats
Matyushov, Dmitry V., and Newton, Marshall D. Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents. United States: N. p., 2017.
Web. doi:10.1021/acs.jpca.7b00414.
Matyushov, Dmitry V., & Newton, Marshall D. Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents. United States. https://doi.org/10.1021/acs.jpca.7b00414
Matyushov, Dmitry V., and Newton, Marshall D. Thu .
"Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents". United States. https://doi.org/10.1021/acs.jpca.7b00414. https://www.osti.gov/servlets/purl/1345838.
@article{osti_1345838,
title = {Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents},
author = {Matyushov, Dmitry V. and Newton, Marshall D.},
abstractNote = {Solvent-induced shift of optical transition lines is traditionally described by the Lippert–McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. We have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived, and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for the reaction field of permanent dipoles in the Lippert–McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert–McRae equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, nonadditive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Lastly, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert–McRae formula.},
doi = {10.1021/acs.jpca.7b00414},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 11,
volume = 121,
place = {United States},
year = {Thu Mar 09 00:00:00 EST 2017},
month = {Thu Mar 09 00:00:00 EST 2017}
}
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