Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Nonadiabatic Molecular Dynamics Simulations Based on Time-Dependent Density Functional Tight-Binding Method

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0100339· OSTI ID:1879390
 [1];  [2];  [3];  [4];  [3];  [1];  [3]
  1. Shenzhen JL Computational Science and Applied Research Institute (China)
  2. Huaiyin Normal Univ., Huaian (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Shenzhen JL Computational Science and Applied Research Institute (China); Beijing Computational Science Research Center (China); Univ. of Bremen (Germany)
+ Show Author Affiliations
Nonadiabatic excited-state molecular dynamics underpin many photophysical and photochemical phenomena, such as exciton dynamics, charge separation and transport. In this work, we present an efficient nonadiabatic molecular dynamic (NAMD) simulation method based on time-dependent density functional tight-binding (TDDFTB) theory. Specifically, the adiabatic electronic structure, an essential NAMD input, is described at the TDDFTB level. Here, the nonadiabatic effects originating from the coupled motions of electrons and nuclei are treated by the trajectory surface hopping algorithm. To improve the computational efficiency, nonadiabatic couplings between excited states within the TDDFTB method are derived and implemented using an analytical approach. Further, the time-dependent nonadiabatic coupling scalars are calculated based on the overlap between molecular orbitals rather than the Slater determinants to speed up the simulations. In addition, the electronic decoherence scheme and a state reassigned unavoided crossings algorithm, which has been implemented in the NEXMD software, are used to improve the accuracy of the simulated dynamics and handle trivial unavoided crossings. Finally, the photoinduced nonadiabatic dynamics of a benzene molecule are simulated to demonstrate our implementation. The results for excited state NAMD simulations of benzene molecule based on TDDFTB method compare well that obtained with numerically expensive time-dependent density functional theory. The proposed methodology provides an attractive theoretical simulation tool for predicting the photophysical and photochemical properties of complex materials.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
Guangdong Shenzhen Joint Key Fund; National Natural Science Foundation of China (NSFC); Shenzhen Basic Research Fund; Sino-German Mobility Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
89233218CNA000001; SC0019484
OSTI ID:
1879390
Report Number(s):
LA-UR-21-32095
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 157; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (92)

Charge and Energy Transfer Dynamics in Molecular Systems book January 2003
Mechanistic Studies of Plasmon Chemistry on Metal Catalysts journal February 2019
Auf dem Weg zu makrocyclischenpara-Phenylenen journal July 1993
Relevance of Electron-Driven Proton-Transfer Processes for the Photostability of Proteins journal February 2006
Trajectory-Based Nonadiabatic Dynamics with Time-Dependent Density Functional Theory journal April 2013
Analytical excited state forces for the time-dependent density-functional tight-binding method journal January 2007
Range separated functionals in the density functional based tight-binding method: Formalism journal December 2011
A perspective on the CASPT2 method journal April 2011
Newton-X: a surface-hopping program for nonadiabatic molecular dynamics: Newton-X
  • Barbatti, Mario; Ruckenbauer, Matthias; Plasser, Felix
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1158
journal June 2013
Nonadiabatic dynamics: The SHARC approach
  • Mai, Sebastian; Marquetand, Philipp; González, Leticia
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6 https://doi.org/10.1002/wcms.1370
journal May 2018
Spectrum simulation and decomposition with nuclear ensemble: formal derivation and application to benzene, furan and 2-phenylfuran book June 2012
Bemerkung �ber die angen�herte G�ltigkeit der klassischen Mechanik innerhalb der Quantenmechanik journal July 1927
The second-order Ehrenfest method journal June 2014
Direct minimization in mc scf theory. the quasi-newton method journal October 1981
Implementation of surface hopping molecular dynamics using semiempirical methods journal June 2008
DFTBaby: A software package for non-adiabatic molecular dynamics simulations based on long-range corrected tight-binding TD-DFT(B) journal December 2017
The on-the-fly surface-hopping program system Newton-X: Application to ab initio simulation of the nonadiabatic photodynamics of benchmark systems journal August 2007
Approximate time-dependent density functional theory journal November 2009
Constant temperature simulations using the Langevin equation with velocity Verlet integration journal September 1998
Modeling Non-adiabatic Dynamics in Nanoscale and Condensed Matter Systems journal November 2021
Surface-Plasmon-Driven Hot Electron Photochemistry journal November 2017
Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials journal February 2020
NEXMD Software Package for Nonadiabatic Excited State Molecular Dynamics Simulations journal July 2020
First Principles Nonadiabatic Excited-State Molecular Dynamics in NWChem journal August 2020
PySpawn: Software for Nonadiabatic Quantum Molecular Dynamics journal July 2020
An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem journal May 2021
An Efficient, Augmented Surface Hopping Algorithm That Includes Decoherence for Use in Large-Scale Simulations journal October 2016
Time-Dependent Extension of the Long-Range Corrected Density Functional Based Tight-Binding Method journal March 2017
Nonadiabatic Dynamics of Cycloparaphenylenes with TD-DFTB Surface Hopping journal November 2017
Quadratic Response Properties from TDDFT: Trials and Tribulations journal December 2017
A Real-Time Time-Dependent Density Functional Tight-Binding Implementation for Semiclassical Excited State Electron–Nuclear Dynamics and Pump–Probe Spectroscopy Simulations journal June 2020
Real-Time Electron Dynamics Study of Plasmon-Mediated Photocatalysis on an Icosahedral Al 13 –1 Nanocluster journal May 2021
Atomistic Insights into Chemical Interface Damping of Surface Plasmon Excitations in Silver Nanoclusters journal October 2016
A Nonadiabatic Excited State Molecular Mechanics/Extended Hückel Ehrenfest Method journal November 2016
Nonadiabatic Molecular Dynamics Simulation of Charge Separation and Recombination at a WS2/QD Heterojunction journal March 2018
TD-DFT and TD-DFTB Investigation of the Optical Properties and Electronic Structure of Silver Nanorods and Nanorod Dimers journal June 2018
The Rise of Neural Networks for Materials and Chemical Dynamics journal July 2021
Fast Numerical Evaluation of Time-Derivative Nonadiabatic Couplings for Mixed Quantum–Classical Methods journal October 2015
The Simplest Possible Approach for Simulating S 0 – S 1 Conical Intersections with DFT/TDDFT: Adding One Doubly Excited Configuration journal May 2019
Direct Photocatalysis by Plasmonic Nanostructures journal December 2013
Parametrization and Benchmark of DFTB3 for Organic Molecules journal November 2012
Extensions of the Time-Dependent Density Functional Based Tight-Binding Approach journal October 2013
Automated Search for Minimum Energy Conical Intersection Geometries between the Lowest Two Singlet States S 0 /S 1 -MECIs by the Spin-Flip TDDFT Method journal August 2013
The PYXAID Program for Non-Adiabatic Molecular Dynamics in Condensed Matter Systems journal October 2013
Advanced Capabilities of the PYXAID Program: Integration Schemes, Decoherence Effects, Multiexcitonic States, and Field-Matter Interaction journal January 2014
Modified Ehrenfest Formalism for Efficient Large-Scale ab initio Molecular Dynamics journal March 2009
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations journal December 1992
Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model journal June 1985
Mechanistic Insights into Photocatalyzed H 2 Dissociation on Au Clusters journal July 2020
Nonadiabatic Molecular Dynamics Simulation of Light-Induced Electron Transfer from an Anchored Molecular Electron Donor to a Semiconductor Acceptor † journal August 2002
Graphene Nanoflakes: Thermal Stability, Infrared Signatures, and Potential Applications in the Field of Spintronics and Optical Nanodevices journal September 2010
Analysis of State-Specific Vibrations Coupled to the Unidirectional Energy Transfer in Conjugated Dendrimers journal October 2012
Nonadiabatic Molecular Dynamics Modeling of the Intrachain Charge Transport in Conjugated Diketopyrrolo-pyrrole Polymers journal March 2014
Derivative Couplings between Time-Dependent Density Functional Theory Excited States in the Random-Phase Approximation Based on Pseudo-Wavefunctions: Behavior around Conical Intersections journal August 2014
Detailed Dynamics of the Nonradiative Deactivation of Adenine: A Semiclassical Dynamics Study journal August 2008
Localization of Electronic Excitations in Conjugated Polymers Studied by DFT journal February 2011
Self-Trapping of Excitons, Violation of Condon Approximation, and Efficient Fluorescence in Conjugated Cycloparaphenylenes journal October 2014
Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures journal May 2011
Identifying electron transfer coordinates in donor-bridge-acceptor systems using mode projection analysis journal February 2017
Coherent exciton-vibrational dynamics and energy transfer in conjugated organics journal June 2018
Plasmon-driven sub-picosecond breathing of metal nanoparticles journal January 2017
Charge transfer dynamics at the boron subphthalocyanine chloride/C 60 interface: non-adiabatic dynamics study with Libra-X journal January 2018
Highlights from Faraday Discussion 300: hot electron science and microscopic processes in plasmonics and catalysis, London, UK, February 2019 journal January 2019
Non-adiabatic molecular dynamics investigation of the size dependence of the electronic relaxation in polyacenes journal January 2019
Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation journal January 2019
Plasmon-induced hot-carrier generation differences in gold and silver nanoclusters journal January 2019
Direct semiclassical simulation of photochemical processes with semiempirical wave functions journal June 2001
Adiabatic time-dependent density functional methods for excited state properties journal October 2002
Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H + with D 2 journal July 1971
Ab initio Ehrenfest dynamics journal August 2005
First-order nonadiabatic couplings from time-dependent hybrid density functional response theory: Consistent formalism, implementation, and performance journal January 2010
Including quantum decoherence in surface hopping journal October 2010
Long-range corrected hybrid functionals for π-conjugated systems: Dependence of the range-separation parameter on conjugation length journal November 2011
Nonadiabatic Ehrenfest molecular dynamics within the projector augmented-wave method journal April 2012
Molecular dynamics with electronic transitions journal July 1990
Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules journal July 2012
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
Decoherence-induced surface hopping journal December 2012
Perspective: Nonadiabatic dynamics theory journal December 2012
Ultrafast internal conversion and photodissociation of molecules excited by femtosecond 155 nm laser pulses journal October 1999
Nonadiabatic excited-state molecular dynamics: Treatment of electronic decoherence journal June 2013
First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels journal July 2014
First order nonadiabatic coupling matrix elements between excited states: Implementation and application at the TD-DFT and pp-TDA levels journal December 2014
Implementation and benchmark of a long-range corrected functional in the density functional based tight-binding method journal November 2015
Unphysical divergences in response theory journal October 2016
TheoDORE: A toolbox for a detailed and automated analysis of electronic excited state computations journal February 2020
DFTB+, a software package for efficient approximate density functional theory based atomistic simulations journal March 2020
Nonadiabatic dynamics with spin-flip vs linear-response time-dependent density functional theory: A case study for the protonated Schiff base C5H6NH2+ journal September 2021
Conical intersections and double excitations in time-dependent density functional theory journal March 2006
On the Quantum Correction For Thermodynamic Equilibrium journal June 1932
Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties journal September 1998
Trajectory Surface Hopping within Linear Response Time-Dependent Density-Functional Theory journal January 2007

Similar Records

Nonadiabatic Excited-State Molecular Dynamics for Open-Shell Systems
Journal Article · Sun Mar 01 19:00:00 EST 2020 · Journal of Chemical Theory and Computation · OSTI ID:1614840
First Principles Nonadiabatic Excited-State Molecular Dynamics in NWChem
Journal Article · Mon Aug 17 20:00:00 EDT 2020 · Journal of Chemical Theory and Computation · OSTI ID:1686097
Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics
Journal Article · Mon Jul 14 20:00:00 EDT 2025 · The Journal of Physical Chemistry A · OSTI ID:2575648

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Density functional tight-binding
Non-adiabatic molecular dynamics