Access count of this item: 186

Files in This Item:
File Description SizeFormat 
1.4899049.pdf1.14 MBAdobe PDFView/Open
Title: Optimizing minimum free-energy crossing points in solution: Linear-response free energy/spin-flip density functional theory approach.
Authors: Minezawa, Noriyuki
Author's alias: 嶺澤, 範行
Issue Date: 28-Oct-2014
Publisher: American Institute of Physics Inc.
Journal title: The Journal of chemical physics
Volume: 141
Issue: 16
Thesis number: 164118
Abstract: Examining photochemical processes in solution requires understanding the solvent effects on the potential energy profiles near conical intersections (CIs). For that purpose, the CI point in solution is determined as the crossing between nonequilibrium free energy surfaces. In this work, the nonequilibrium free energy is described using the combined method of linear-response free energy and collinear spin-flip time-dependent density functional theory. The proposed approach reveals the solvent effects on the CI geometries of stilbene in an acetonitrile solution and those of thymine in water. Polar acetonitrile decreases the energy difference between the twisted minimum and twisted-pyramidalized CI of stilbene. For thymine in water, the hydrogen bond formation stabilizes significantly the CI puckered at the carbonyl carbon atom. The result is consistent with the recent simulation showing that the reaction path via this geometry is open in water. Therefore, the present method is a promising way of identifying the free-energy crossing points that play an essential role in photochemistry of solvated molecules.
Rights: Copyright 2014 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
DOI(Published Version): 10.1063/1.4899049
PubMed ID: 25362283
Appears in Collections:Journal Articles

Show full item record

Export to RefWorks

Export Format: 

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.