Extended Lagrangian Excited State Molecular Dynamics

J. A. Bjorgaard, D. Sheppard, S. Tretiak, A. M.N. Niklasson

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


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).

Original languageEnglish
Pages (from-to)799-806
Number of pages8
JournalJournal of Chemical Theory and Computation
Issue number2
Publication statusPublished - 13 Feb 2018
Externally publishedYes


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