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  4. Analytic first derivatives of floating occupation molecular orbital-complete active space configuration interaction on graphical processing units
 
research article

Analytic first derivatives of floating occupation molecular orbital-complete active space configuration interaction on graphical processing units

Hohenstein, Edward G.
•
Bouduban, Marine E. F.  
•
Song, Chenchen
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2015
Journal Of Chemical Physics

The floating occupation molecular orbital-complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the state-averaged complete active space self-consistent field (SA-CASSCF) method. We have formulated the analytic first derivative of FOMO-CASCI in a manner that is well-suited for a highly efficient implementation using graphical processing units (GPUs). Using this implementation, we demonstrate that FOMO-CASCI gradients are of similar computational expense to configuration interaction singles (CIS) or time-dependent density functional theory (TDDFT). In contrast to CIS and TDDFT, FOMO-CASCI can describe multireference character of the electronic wavefunction. We show that FOMO-CASCI compares very favorably to SA-CASSCF in its ability to describe molecular geometries and potential energy surfaces around minimum energy conical intersections. Finally, we apply FOMO-CASCI to the excited state hydrogen transfer reaction in methyl salicylate. (C) 2015 AIP Publishing LLC.

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Type
research article
DOI
10.1063/1.4923259
Web of Science ID

WOS:000357873900015

Author(s)
Hohenstein, Edward G.
Bouduban, Marine E. F.  
Song, Chenchen
Luehr, Nathan
Ufimtsev, Ivan S.
Martinez, Todd J.
Date Issued

2015

Publisher

Amer Inst Physics

Published in
Journal Of Chemical Physics
Volume

143

Issue

1

Article Number

014111

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
GR-MO  
Available on Infoscience
September 28, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/118950
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