Extended Lagrangian Excited State Molecular Dynamics

An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100,...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2018-02, Vol.14 (2), p.799-806
Main Authors: Bjorgaard, J. A, Sheppard, D, Tretiak, S, Niklasson, A. M. N
Format: Article
Language:English
Subjects:
Computer simulation
Configuration interaction
Density functional theory
extended lagrangian
Field theory
Formulations
Ground state
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Iterative methods
Lagrangian function
Mathematical models
MATHEMATICS AND COMPUTING
Molecular chains
Molecular dynamics
Time dependence
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Summary:An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. The XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.7b00857