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Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states

Journal Article · · Chemical Physics
 [1];  [2];  [3];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Skolkovo Inst. of Science and Technology, Moscow (Russian Federation)
  3. National Univ. of Quilmes, Buenos Aires (Argentina)
+ Show Author Affiliations
The simulation of nonadiabatic dynamics in extended molecular systems involving hundreds of atoms and large densities of states is particularly challenging. Nonadiabatic coupling terms (NACTs) represent a significant numerical bottleneck in surface hopping approaches. Rather than using unreliable NACT cutting schemes, here we develop “on-the-fly” state limiting methods to eliminate states that are no longer essential for the non-radiative relaxation dynamics as a trajectory proceeds. Here, we propose a state number criteria and an energy-based state limit. The latter is more physically relevant by requiring a user-imposed energy threshold. For this purpose, we introduce a local kinetic energy gauge by summing contributions from atoms within the spatial localization of the electronic wavefunction to define the energy available for upward hops. The proposed state limiting schemes are implemented within the nonadiabatic excited-state molecular dynamics framework to simulate photoinduced relaxation in poly-phenylene vinylene (PPV) and branched poly-phenylene ethynylene (PPE) oligomers for benchmark evaluation.
Research Organization:
Los Alamos National Laboratory (LANL)
Sponsoring Organization:
National Promotion Agency Scientific and Technological (ANPCyT); National Scientific and Technical Research Council (CONICET); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1458930
Alternate ID(s):
OSTI ID: 22644520
OSTI ID: 1396782
Report Number(s):
LA-UR-16-21401
Journal Information:
Chemical Physics, Journal Name: Chemical Physics Journal Issue: C Vol. 481; ISSN 0301-0104
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Modeling nonadiabatic dynamics in condensed matter materials: some recent advances and applications journal November 2019

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
NA-ESMD
fewest switches surface hopping
local kinetic energy
poly-phenylene ethynylene
poly-phenylene vinylene
state reduction