Communication: Proper treatment of classically forbidden electronic transitions significantly improves detailed balance in surface hopping | Zendy

Andrew E. Sifain | Zendy; Linjun Wang | Zendy; Oleg V. Prezhdo | Zendy

Open Access

Communication: Proper treatment of classically forbidden electronic transitions significantly improves detailed balance in surface hopping

Author(s) -

Andrew E. Sifain,

Linjun Wang,

Oleg V. Prezhdo

Publication year - 2016

Publication title -

the journal of chemical physics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.071

H-Index - 357

eISSN - 1089-7690

pISSN - 0021-9606

DOI - 10.1063/1.4953444

Subject(s) - surface hopping , detailed balance , convergence (economics) , physics , boltzmann constant , thermal equilibrium , statistical physics , trajectory , thermal , balance (ability) , quantum , quantum mechanics , thermodynamics , medicine , physical medicine and rehabilitation , economics , economic growth

Surface hopping is the most popular method for nonadiabatic molecular dynamics. Many have reported that it does not rigorously attain detailed balance at thermal equilibrium, but does so approximately. We show that convergence to the Boltzmann populations is significantly improved when the nuclear velocity is reversed after a classically forbidden hop. The proposed prescription significantly reduces the total number of classically forbidden hops encountered along a trajectory, suggesting that some randomization in nuclear velocity is needed when classically forbidden hops constitute a large fraction of attempted hops. Our results are verified computationally using two- and three-level quantum subsystems, coupled to a classical bath undergoing Langevin dynamics.

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