On the Generation of Electronic Ring Currents under Vibronic Coupling Effects

TL;DR

This paper investigates how vibronic coupling influences electronic ring currents generated by circularly polarized light, revealing that nonadiabatic effects significantly affect current magnitude and behavior even in simple models.

Contribution

Introduces a solvable model to analyze vibronic effects on electronic ring currents, highlighting their importance beyond the Born-Oppenheimer approximation.

Findings

Vibronic coupling significantly affects ring current strength.

Maximum current depends on nonadiabatic interaction strength.

Ring currents vanish in the Born-Oppenheimer limit.

Abstract

We study the generation of electronic ring currents in the presence of nonadiabatic coupling using circularly polarized light. For this, we introduce a solvable model consisting of an electron and a nucleus rotating around a common center and subject to their mutual Coulomb interaction. The simplicity of the model brings to the forefront the non-trivial properties of electronic ring currents in the presence of coupling to the nuclear coordinates and enables the characterization of various limiting situations transparently. Employing this model, we show that vibronic coupling effects play a crucial role even when a single $E$ degenerate eigenstate of the system supports the current. The maximum current of a degenerate eigenstate depends on the strength of the nonadiabatic interactions. In the limit of large nuclear to electronic masses, in which the Born-Oppenheimer approximation becomes exact, constant ring currents and time-averaged oscillatory currents necessarily vanish.