Nonadiabatic molecular dynamics (NA-MD) is an extremely useful approach to model electron transfer dynamics in molecular and solid state systems. The performance of NA-MD simulations depends critically on the accuracy of the underlying electronic structure properties, such as state energies and nonadiabatic couplings (NAC). Practical NA-MD modeling relies extensively on computationally efficient pure density functionals, despite the known intrinsic problems of the latter. Hybrid functionals are significantly more expensive, but are supposedly more reliable. In this presentation, I will showcase how the choice of the density functional affects the magnitudes of computed NACs. The focus will be on small silicon clusters and silicon hydrides. The role of correct asymptotic of exchange will be emphasized and the implications of the incorrect behavior of pure density functionals on the computed NACs will be discussed.

Nonadiabatic couplings and the choice of density functional: Exchange cannot be neglected

253rd National Meeting (2017)

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