Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

7-2011

Journal or Book Title

Journal of Physical Chemistry A

Volume

115

Issue

35

First Page

9801

Last Page

9809

DOI

10.1021/jp2045564

Abstract

The combined time-dependent density functional theory effective fragment potential method (TDDFT/EFP1) is applied to a study of the solvent-induced shift of the lowest singlet π → π* charge-transfer excited state of p-nitroaniline (pNA) from the gas to the condensed phase in water. Molecular dynamics simulations of pNA with 150 EFP1 water molecules are used to model the condensed-phase and generate a simulated spectrum of the lowest singlet charge-transfer excitation. The TDDFT/EFP1 method successfully reproduces the experimental condensed-phase π → π* vertical excitation energy and solvent-induced red shift of pNA in water. The largest contribution to the red shift comes from Coulomb interactions, betweenpNA and water, and solute relaxation. The solvent shift contributions reflect the increase in zwitterionic character of pNA upon solvation.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 115 (2011): 9801, doi:10.1021/jp2045564. Copyright 2011 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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