Nonadiabatic Excited-State Molecular Dynamics for Open-Shell Systems

Zhang, Yu; Li, Linqiu; Tretiak, Sergei; Nelson, Tammie Renee

doi:10.1021/acs.jctc.9b00928

Nonadiabatic Excited-State Molecular Dynamics for Open-Shell Systems

Journal Article · Sun Mar 01 23:00:00 EST 2020 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.9b00928· OSTI ID:1614840

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of Southern California, Los Angeles, CA (United States)

Nonadiabatic Molecular Dynamics (NAMD) of excited states has been widely used in the simulation of photoinduced phenomena. However, the inability to treat bond breaking and forming processes with single-reference electronic structure methods limits their application in photochemistry for extended molecular systems. In this work, the extension of excited-state NAMD for open-shell systems is developed and implemented in the NEXMD software. We present the spin-unrestricted CIS and TDSCF formalism for the ground and excited states, analytical derivatives, and nonadiabatic derivative couplings for the respective potential energy surfaces. Next, this methodology is employed to study the photochemical reaction of three model molecules. The results demonstrate the advantage of the open-shell approach in modeling photochemical reactions, especially involving bond breaking processes. We find that the open-shell method lowers the reaction barrier at the bond-breaking limits resulting in larger calculated photochemical quantum yields compared to the respective closed-shell results. We also address problems related to spin contamination in the open-shell method, especially when molecular geometries are far from equilibrium.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1614840

Report Number(s):: LA-UR--19-29917

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 4 Vol. 16; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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