Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

10-2009

Journal or Book Title

Journal of Physical Chemistry A

Volume

113

Issue

46

First Page

12749

Last Page

12753

DOI

10.1021/jp908032x

Abstract

Conical intersections (CIs) of ethylene have been successfully determined using spin-flip density functional theory (SFDFT) combined with a penalty-constrained optimization method. We present in detail three structures, twisted-pyramidalized, hydrogen-migrated, and ethylidene CIs. In contrast to the linear response time-dependent density functional theory, which predicts a purely twisted geometry without pyramidalization as the S1 global minimum, SFDFT gives a pyramidalized structure. Therefore, this is the first correct optimization of CI points of twisted ethylene by the DFT method. The calculated energies and geometries are in good agreement with those obtained by the multireference configuration interaction (MR-CI) method and the multistate formulation of second-order multireference perturbation theory (MS-CASPT2).

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 113 (2009): 12749, doi:10.1021/jp908032x. Copyright 2009 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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