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First Principles Nonadiabatic Excited-State Molecular Dynamics in NWChem

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [1];  [3];  [4];  [5];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Naval Research Lab. (NRL), Washington, DC (United States)
  3. Univ. of Minnesota, Minneapolis, MN (United States)
  4. Univ. of California, Irvine, CA (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations
Computational simulation of non-adiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons, to name a few. Here, we report an implementation of the fewest-switches surface hopping algorithm in the NWChem computational chemistry program. Here the surface hopping method is combined with linear-response time-dependent density functional theory calculations of adiabatic excited state potential energy surfaces. To treat quantum transitions between arbitrary electronic Born{Oppenheimer states, we have implemented both numerical and analytical differentiation schemes for derivative non-adiabatic couplings. A numerical approach for the time-derivative non-adiabatic couplings together with an analytical method for calculating non-adiabatic coupling vectors is an efficient combination for surface hopping approaches. Additionally, electronic decoherence schemes and a state reassigned unavoided crossings algorithm are also implemented to improve the accuracy of the simulated dynamics and to handle trivial unavoided crossings. We apply our code to study the ultrafast decay of photoexcited benzene, including a detailed analysis of the potential energy surface, population decay time scales, and vibrational coordinates coupled to the excitation dynamics. The development presented in this work is a baseline for future implementations of more sophisticated frameworks for simulating of non-adiabatic molecular dynamics in NWChem.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
89233218CNA000001; AC05-76RL01830; SC0008666; SC0019484
OSTI ID:
1686097
Alternate ID(s):
OSTI ID: 1739989
Report Number(s):
LA-UR--20-22739; PNNL-SA--152225
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 16; 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
TDDFT
ab-initio
excited-state
nonadiabatic molecular dynamics
photoexcitation dynamics
surface hopping