Campus Units
Chemistry
Document Type
Article
Publication Version
Published Version
Publication Date
6-2011
Journal or Book Title
Journal of Physical Chemistry A
Volume
115
Issue
27
First Page
7901
Last Page
7911
DOI
10.1021/jp203803a
Abstract
The photoisomerization process of 1,2-diphenylethylene (stilbene) is investigated using the spin-flip density functional theory (SFDFT), which has recently been shown to be a promising approach for locating conical intersection (CI) points (Minezawa, N.; Gordon, M. S. J. Phys. Chem. A2009, 113, 12749). The SFDFT method gives valuable insight into twisted stilbene to which the linear response time-dependent DFT approach cannot be applied. In contrast to the previous SFDFT study of ethylene, a distinct twisted minimum is found for stilbene. The optimized structure has a sizable pyramidalization angle and strong ionic character, indicating that a purely twisted geometry is not a true minimum. In addition, the SFDFT approach can successfully locate two CI points: the twisted-pyramidalized CI that is similar to the ethylene counterpart and another CI that possibly lies on the cyclization pathway of cis-stilbene. The mechanisms of the cis–trans isomerization reaction are discussed on the basis of the two-dimensional potential energy surface along the twisting and pyramidalization angles.
Copyright Owner
American Chemical Society
Copyright Date
2011
Language
en
File Format
application/pdf
Recommended Citation
Minezawa, Noriyuki and Gordon, Mark S., "Photoisomerization of Stilbene: A Spin-Flip Density Functional Theory Approach" (2011). Chemistry Publications. 555.
https://lib.dr.iastate.edu/chem_pubs/555
Comments
Reprinted (adapted) with permission from Journal of Physical Chemistry A 115 (2011): 7901, doi:10.1021/jp203803a. Copyright 2011 American Chemical Society.