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Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3]
  1. Univ. of Chicago, IL (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations
Herein, we present the first implementation of multiconfiguration pair-density functional theory (MC-PDFT) ab initio molecular dynamics. MC-PDFT is a multireference electronic structure method that in many cases has a similar accuracy (or even better accuracy) the complete active space second-order perturbation theory (CASPT2) at a significantly lower computational cost. In this study, we introduced MC-PDFT analytical gradients into the SHARC molecular dynamics program for ab initio, nonadiabatic molecular dynamics simulations. We verify our implementation by examining the intersystem crossing dynamics of thioformaldehyde, and we observe excellent agreement with recent CASPT2 and experimental findings. Moreover, with MC-PDFT, we could perform dynamics simulations with the 12 electron in 10 orbitals active space that was computationally too expensive for direct dynamics with CASPT2.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC); University of Chicago Research Computing Center (RCC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1962830
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 18; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical calculations
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