Electronic Flux Density beyond the Born–Oppenheimer Approximation
| Autor: | E. K. U. Gross, Federica Agostini, Axel Schild |
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| Rok vydání: | 2016 |
| Předmět: |
Physics
010304 chemical physics Born–Huang approximation Diabatic Born–Oppenheimer approximation Electronic structure Electron 01 natural sciences symbols.namesake Quantum electrodynamics 0103 physical sciences symbols Perturbation theory (quantum mechanics) Physical and Theoretical Chemistry Atomic physics 010306 general physics Ground state Wave function |
| Zdroj: | The Journal of Physical Chemistry A. 120:3316-3325 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.5b12657 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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