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Title: 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), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); National Scientific and Technical Research Council (CONICET); National Promotion Agency Scientific and Technological (ANPCyT)
Grant/Contract Number:
AC52-06NA25396; PICT-2010-2375
OSTI ID:
1458930
Alternate ID(s):
OSTI ID: 1396782
Report Number(s):
LA-UR-16-21401; TRN: US1901527
Journal Information:
Chemical Physics, Vol. 481, Issue C; ISSN 0301-0104
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (38)

Molecular dynamics with electronic transitions journal July 1990
Surface hopping dynamics using a locally diabatic formalism: Charge transfer in the ethylene dimer cation and excited state dynamics in the 2-pyridone dimer journal December 2012
Theoretical Insights into Photoinduced Charge Transfer and Catalysis at Oxide Interfaces journal December 2012
Photoexcited Energy Transfer in a Weakly Coupled Dimer journal December 2014
Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers journal December 2012
Conformational disorder in energy transfer: beyond Förster theory journal January 2013
Proton transfer in solution: Molecular dynamics with quantum transitions journal September 1994
Comparison of surface hopping and mean field approaches for model proton transfer reactions journal June 1999
Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations journal January 2015
Trajectory surface hopping study of the O( 3 P) + C 2 H 2 reaction dynamics: Effect of collision energy on the extent of intersystem crossing journal January 2014
Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O( 3 P) + Ethylene Reaction at High Collision Energy journal October 2015
Photochemical reactions in biological systems: probing the effect of the environment by means of hybrid quantum chemistry/molecular mechanics simulations journal January 2012
The Theoretical Estimation of the Bioluminescent Efficiency of the Firefly via a Nonadiabatic Molecular Dynamics Simulation journal January 2015
Nonadiabatic Excited-State Molecular Dynamics Modeling of Photoinduced Dynamics in Conjugated Molecules journal May 2011
Nonadiabatic Excited-State Molecular Dynamics: Modeling Photophysics in Organic Conjugated Materials journal February 2014
On the density matrix based approach to time-dependent density functional response theory journal April 2001
Adiabatic time-dependent density functional methods for excited state properties journal October 2002
Resonant nonlinear polarizabilities in the time-dependent density functional theory journal November 2003
Density-matrix representation of nonadiabatic couplings in time-dependent density functional (TDDFT) theories journal February 2000
Electronic density-matrix algorithm for nonadiabatic couplings in molecular dynamics simulations journal January 2001
Optimization of mixed quantum-classical dynamics: Time-derivative coupling terms and selected couplings journal February 2009
Nonadiabatic Deactivation of 9 H -Adenine: A Comprehensive Picture Based on Mixed Quantum−Classical Dynamics journal May 2008
Nonadiabatic excited-state molecular dynamics: Numerical tests of convergence and parameters journal February 2012
Nonadiabatic excited-state molecular dynamics: Treatment of electronic decoherence journal June 2013
Analysis of State-Specific Vibrations Coupled to the Unidirectional Energy Transfer in Conjugated Dendrimers journal October 2012
Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A journal December 2015
Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules journal July 2012
Artifacts due to trivial unavoided crossings in the modeling of photoinduced energy transfer dynamics in extended conjugated molecules journal December 2013
Signature of Nonadiabatic Coupling in Excited-State Vibrational Modes journal June 2014
Simulations of fluorescence solvatochromism in substituted PPV oligomers from excited state molecular dynamics with implicit solvent journal July 2015
Density Matrix Analysis and Simulation of Electronic Excitations in Conjugated and Aggregated Molecules journal September 2002
Electronic Coherence and Collective Optical Excitations of Conjugated Molecules journal August 1997
Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model journal June 1985
Improvement of the Internal Consistency in Trajectory Surface Hopping journal November 1999
A semiclassical approach to intense-field above-threshold dissociation in the long wavelength limit. II. Conservation principles and coherence in surface hopping journal October 1998
Constant temperature simulations using the Langevin equation with velocity Verlet integration journal September 1998
Ultrafast Spectroscopy of Even-Parity States in π -Conjugated Polymers journal September 2000
Coulomb interactions and linear, nonlinear, and triplet absorption in poly(para-phenylenevinylene) journal January 1997

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