We present an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) intended for single-reference time-dependent ab initio methods. This formulation is a generalization of the extended Lagrangian ground state Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 100, 123004 (2008)]. An implemention is demonstrated using a time-dependent semiempirical method which shows enhanced energy stability and a reduced computational cost. Using this technique, relaxed convergence criteria can 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. We show how this method can be used to reach experimentally relevant time scales for excited state molecular dynamics.

Accelerating excited state molecular dynamics using an extended Lagrangian

255th National Meeting (2018)

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