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Title: An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. National Univ. of Quilmes, Bernal (Argentina)
  3. Univ. of California, Irvine, CA (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations

The recently developed ab-initio multiple cloning (AIMC) approach based on the multicongurational Ehrenfest (MCE) method provides a powerful and accurate way of describing the excited-state dynamics of molecular systems. The AIMC method is a controlled approximation to non-adiabatic dynamics with a particular strength in the proper description of decoherence effects due to branching of vibrational wavepackets at a level crossing. Here we report a new implementation of the AIMC algorithm in the open source NWChem computational chemistry program. The framework combines linear-response time-dependent density functional theory with Ehrenfest mean-eld theory to determine the equations of motion for classical trajectories. The multi-dimensional wave function is decomposed into a superposition of Gaussian coherent states guided by Ehrenfest trajectories (i.e., MCE approach), which can clone with fully quantum mechanical amplitudes and phases. By using an efficient time-derivative based non-adiabatic coupling approach within the AIMC method, all observable are calculated on-the-y in the non-adiabatic molecular dynamics process. As a representative example, we apply our implementation to study the ultrafast photoinduced electronic and vibrational energy transfer in a pyridine molecule. The effects of the cloning procedure on electronic and vibrational coherence, relaxation and unidirectional energy transfer are discussed. This new AIMC implementation provides a high-level non-adiabatic molecular dynamics framework for simulating photoexcited dynamics in complex molecular systems and experimentally relevant ultrafast spectroscopic probes, such as nonlinear coherent optical and X-ray signals.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Scientific and Technical Research Council (CONICET)
Grant/Contract Number:
AC05-76RL01830; KC0301030; KC030103172684; SC0019484; PICT-2018-2360; 89233218CNA000001
OSTI ID:
1808061
Alternate ID(s):
OSTI ID: 1810557; OSTI ID: 1819159
Report Number(s):
PNNL-SA-159312; LA-UR-21-22236
Journal Information:
Journal of Chemical Theory and Computation, Vol. 17, Issue 6; 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
Wave function
Electrical energy
Genetics
Computational chemistry
Excited states