Simulating Electron Dynamics of Complex Molecules with TimeDependent Complete Active Space Configuration Interaction
Abstract
In this paper, timedependent electronic structure methods are growing in popularity as tools for modeling ultrafast and/or nonlinear processes, for computing spectra, and as the electronic structure component of meanfield molecular dynamics simulations. Timedependent configuration interaction (TDCI) offers several advantages over the widely used realtime timedependent density functional theory: namely, that it correctly models Rabi oscillations; it offers a spinpure description of openshell systems; and a hierarchy of TDCI methods can be defined that systematically approach the exact solution of the timedependent Schrodinger equation (TDSE). In this work, we present a novel TDCI approach that extends TDCI to large complete activespace configuration expansions. Such extension is enabled by use of a direct configuration interaction approach that eliminates the need to explicitly build, store, or diagonalize the Hamiltonian matrix. Graphics processing unit (GPU) acceleration enables fast solution of the TDSE even for large active spaces—up to 12 electrons in 12 orbitals (853776 determinants) in this work. A symplectic split operator propagator yields longtime norm conservation. We demonstrate the applicability of our approach by computing the response of a large molecule with a strongly correlated ground state, decacene (C_{42}H_{24}), to various pulses (δfunction, transform limited, chirped). Our simulations predict that chirped pulsesmore »
 Authors:

 Michigan State Univ., East Lansing, MI (United States)
 Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
 Publication Date:
 Research Org.:
 SLAC National Accelerator Lab., Menlo Park, CA (United States)
 Sponsoring Org.:
 USDOE
 OSTI Identifier:
 1476145
 Grant/Contract Number:
 AC0276SF00515; FA95501710411
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 14; Journal Issue: 8; Journal ID: ISSN 15499618
 Publisher:
 American Chemical Society
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Peng, Wei Tao, Fales, B. Scott, and Levine, Benjamin G. Simulating Electron Dynamics of Complex Molecules with TimeDependent Complete Active Space Configuration Interaction. United States: N. p., 2018.
Web. doi:10.1021/acs.jctc.8b00381.
Peng, Wei Tao, Fales, B. Scott, & Levine, Benjamin G. Simulating Electron Dynamics of Complex Molecules with TimeDependent Complete Active Space Configuration Interaction. United States. doi:10.1021/acs.jctc.8b00381.
Peng, Wei Tao, Fales, B. Scott, and Levine, Benjamin G. Mon .
"Simulating Electron Dynamics of Complex Molecules with TimeDependent Complete Active Space Configuration Interaction". United States. doi:10.1021/acs.jctc.8b00381. https://www.osti.gov/servlets/purl/1476145.
@article{osti_1476145,
title = {Simulating Electron Dynamics of Complex Molecules with TimeDependent Complete Active Space Configuration Interaction},
author = {Peng, Wei Tao and Fales, B. Scott and Levine, Benjamin G.},
abstractNote = {In this paper, timedependent electronic structure methods are growing in popularity as tools for modeling ultrafast and/or nonlinear processes, for computing spectra, and as the electronic structure component of meanfield molecular dynamics simulations. Timedependent configuration interaction (TDCI) offers several advantages over the widely used realtime timedependent density functional theory: namely, that it correctly models Rabi oscillations; it offers a spinpure description of openshell systems; and a hierarchy of TDCI methods can be defined that systematically approach the exact solution of the timedependent Schrodinger equation (TDSE). In this work, we present a novel TDCI approach that extends TDCI to large complete activespace configuration expansions. Such extension is enabled by use of a direct configuration interaction approach that eliminates the need to explicitly build, store, or diagonalize the Hamiltonian matrix. Graphics processing unit (GPU) acceleration enables fast solution of the TDSE even for large active spaces—up to 12 electrons in 12 orbitals (853776 determinants) in this work. A symplectic split operator propagator yields longtime norm conservation. We demonstrate the applicability of our approach by computing the response of a large molecule with a strongly correlated ground state, decacene (C42H24), to various pulses (δfunction, transform limited, chirped). Our simulations predict that chirped pulses can be used to induce dipoleforbidden transitions. Simulations of decacene using the 631G(d) basis set and a 12 electrons/12 orbitals active space took 20.1 h to propagate for 100 fs with a 1 attosecond time step on a single NVIDIA K40 GPU. Convergence with respect to time step is found to depend on the property being computed and the chosen active space.},
doi = {10.1021/acs.jctc.8b00381},
journal = {Journal of Chemical Theory and Computation},
number = 8,
volume = 14,
place = {United States},
year = {2018},
month = {7}
}
Web of Science
Figures / Tables:
Works referencing / citing this record:
Time dependent adaptive configuration interaction applied to attosecond charge migration
journal, November 2019
 Schriber, Jeffrey B.; Evangelista, Francesco A.
 The Journal of Chemical Physics, Vol. 151, Issue 17
The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges
journal, January 2020
 Baiardi, Alberto; Reiher, Markus
 The Journal of Chemical Physics, Vol. 152, Issue 4
Modeling nonadiabatic dynamics in condensed matter materials: some recent advances and applications
journal, November 2019
 Smith, Brendan; Akimov, Alexey V.
 Journal of Physics: Condensed Matter, Vol. 32, Issue 7
Figures / Tables found in this record: