Phase-corrected surface hopping: correcting the phase evolution of the electronic wavefunction.

Published

Journal Article

In this paper, we show that a remarkably simple correction can be made to the equation of motion which governs the evolution of the electronic wavefunction over some prescribed nuclear trajectory in the fewest-switches surface hopping algorithm. This corrected electronic equation of motion can then be used in conjunction with traditional or modified surface hopping methods to calculate nonadiabatic effects in large systems. Although the correction adds no computational cost to the algorithm, it leads to a dramatic improvement in scattering probabilities for all model problems studied thus far. We show that this correction can be applied to one of Tully's original one-dimensional model problems or to a more sophisticated two-dimensional example and yields substantially greater accuracy than the traditional approach.

Full Text

Duke Authors

Cited Authors

  • Shenvi, N; Subotnik, JE; Yang, W

Published Date

  • July 2011

Published In

Volume / Issue

  • 135 / 2

Start / End Page

  • 024101 -

PubMed ID

  • 21766919

Pubmed Central ID

  • 21766919

Electronic International Standard Serial Number (EISSN)

  • 1089-7690

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.3603447

Language

  • eng