Concerted Electronic and Nuclear Fluxes During Coherent Tunnelling in Asymmetric Double-Well Potentials

The Journal of Physical Chemistry. a
Timm BredtmannJian-Ming Zhao

Abstract

The quantum theory of concerted electronic and nuclear fluxes (CENFs) during coherent periodic tunnelling from reactants (R) to products (P) and back to R in molecules with asymmetric double-well potentials is developed. The results are deduced from the solution of the time-dependent Schrödinger equation as a coherent superposition of two eigenstates; here, these are the two states of the lowest tunnelling doublet. This allows the periodic time evolutions of the resulting electronic and nuclear probability densities (EPDs and NPDs) as well as the CENFs to be expressed in terms of simple sinusodial functions. These analytical results reveal various phenomena during coherent tunnelling in asymmetric double-well potentials, e.g., all EPDs and NPDs as well as all CENFs are synchronous. Distortion of the symmetric reference to a system with an asymmetric double-well potential breaks the spatial symmetry of the EPDs and NPDs, but, surprisingly, the symmetry of the CENFs is conserved. Exemplary application to the Cope rearrangement of semibullvalene shows that tunnelling of the ideal symmetric system can be suppressed by asymmetries induced by rather small external electric fields. The amplitude for the half tunnelling, half nontunnel...Continue Reading

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Citations

Apr 6, 2016·The Journal of Physical Chemistry. a·Gunter HermannJean Christophe Tremblay
Oct 28, 2017·Physical Chemistry Chemical Physics : PCCP·Juan AndrésBernard Silvi
Jan 10, 2019·The Journal of Chemical Physics·Csaba FábriMartin Quack
Jun 25, 2021·Chemical Science·Omer KirshenboimSebastian Kozuch

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