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Title: Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method [Non-Adiabatic Ab Initio Molecular Dynamics with Floating Occupation Molecular Orbitals CASCI Method]

Abstract

Here, we show that the floating occupation molecular orbital complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the widely used complete active space self-consistent field (CASSCF) method in direct nonadiabatic dynamics simulations. We have simulated photodynamics of three archetypal molecules in photodynamics: ethylene, methaniminium cation, and malonaldehyde. We compared the time evolution of electronic populations and reaction mechanisms as revealed by the FOMO-CASCI and CASSCF approaches. Generally, the two approaches provide similar results. Some dynamical differences are observed, but these can be traced back to energetically minor differences in the potential energy surfaces. We suggest that the FOMO-CASCI method represents, due to its efficiency and stability, a promising approach for direct ab initio dynamics in the excited state.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4]
  1. Univ. of Chemistry and Technology, Prague (Czech Republic)
  2. The Graduate Center of the City Univ. of New York, New York, NY (United States); Stanford Univ., Stanford, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Chemistry and Technology, Prague (Czech Republic); J. Heyrovsky Institute of Physical Chemistry, Prague 8 (Czech Republic)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1457420
Grant/Contract Number:  
AC02-76SF00515; LH15081; 13-34168S
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 1; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hollas, Daniel, Sistik, Lukas, Hohenstein, Edward G., Martinez, Todd J., and Slavicek, Petr. Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method [Non-Adiabatic Ab Initio Molecular Dynamics with Floating Occupation Molecular Orbitals CASCI Method]. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00958.
Hollas, Daniel, Sistik, Lukas, Hohenstein, Edward G., Martinez, Todd J., & Slavicek, Petr. Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method [Non-Adiabatic Ab Initio Molecular Dynamics with Floating Occupation Molecular Orbitals CASCI Method]. United States. doi:10.1021/acs.jctc.7b00958.
Hollas, Daniel, Sistik, Lukas, Hohenstein, Edward G., Martinez, Todd J., and Slavicek, Petr. Tue . "Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method [Non-Adiabatic Ab Initio Molecular Dynamics with Floating Occupation Molecular Orbitals CASCI Method]". United States. doi:10.1021/acs.jctc.7b00958.
@article{osti_1457420,
title = {Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method [Non-Adiabatic Ab Initio Molecular Dynamics with Floating Occupation Molecular Orbitals CASCI Method]},
author = {Hollas, Daniel and Sistik, Lukas and Hohenstein, Edward G. and Martinez, Todd J. and Slavicek, Petr},
abstractNote = {Here, we show that the floating occupation molecular orbital complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the widely used complete active space self-consistent field (CASSCF) method in direct nonadiabatic dynamics simulations. We have simulated photodynamics of three archetypal molecules in photodynamics: ethylene, methaniminium cation, and malonaldehyde. We compared the time evolution of electronic populations and reaction mechanisms as revealed by the FOMO-CASCI and CASSCF approaches. Generally, the two approaches provide similar results. Some dynamical differences are observed, but these can be traced back to energetically minor differences in the potential energy surfaces. We suggest that the FOMO-CASCI method represents, due to its efficiency and stability, a promising approach for direct ab initio dynamics in the excited state.},
doi = {10.1021/acs.jctc.7b00958},
journal = {Journal of Chemical Theory and Computation},
number = 1,
volume = 14,
place = {United States},
year = {Tue Dec 05 00:00:00 EST 2017},
month = {Tue Dec 05 00:00:00 EST 2017}
}

Journal Article:
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