TY - JOUR

T1 - Electronic Flux Density beyond the Born-Oppenheimer Approximation

AU - Schild, Axel

AU - Agostini, Federica

AU - Gross, E. K.U.

N1 - Publisher Copyright:
© 2016 American Chemical Society.

PY - 2016/5/19

Y1 - 2016/5/19

N2 - In the Born-Oppenheimer approximation, the electronic wave function is typically real-valued and hence the electronic flux density (current density) seems to vanish. This is unfortunate for chemistry, because it precludes the possibility to monitor the electronic motion associated with the nuclear motion during chemical rearrangements from a Born-Oppenheimer simulation of the process. We study an electronic flux density obtained from a correction to the electronic wave function. This correction is derived via nuclear velocity perturbation theory applied in the framework of the exact factorization of electrons and nuclei. To compute the correction, only the ground state potential energy surface and the electronic wave function are needed. For a model system, we demonstrate that this electronic flux density approximates the true one very well, for coherent tunneling dynamics as well as for over-the-barrier scattering, and already for mass ratios between electrons and nuclei that are much larger than the true mass ratios.

AB - In the Born-Oppenheimer approximation, the electronic wave function is typically real-valued and hence the electronic flux density (current density) seems to vanish. This is unfortunate for chemistry, because it precludes the possibility to monitor the electronic motion associated with the nuclear motion during chemical rearrangements from a Born-Oppenheimer simulation of the process. We study an electronic flux density obtained from a correction to the electronic wave function. This correction is derived via nuclear velocity perturbation theory applied in the framework of the exact factorization of electrons and nuclei. To compute the correction, only the ground state potential energy surface and the electronic wave function are needed. For a model system, we demonstrate that this electronic flux density approximates the true one very well, for coherent tunneling dynamics as well as for over-the-barrier scattering, and already for mass ratios between electrons and nuclei that are much larger than the true mass ratios.

UR - http://www.scopus.com/inward/record.url?scp=84971320501&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.5b12657

DO - 10.1021/acs.jpca.5b12657

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AN - SCOPUS:84971320501

SN - 1089-5639

VL - 120

SP - 3316

EP - 3325

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 19

ER -