Is the direct observation of electronic coherence in electron transfer reactions possible?

TL;DR

This paper explores the conditions under which electronic coherence can be observed in electron transfer reactions, emphasizing the importance of initial system preparation and extending theoretical methods to assess experimental feasibility.

Contribution

It introduces an extended formalism and simulations to analyze how initial preparations influence the observability of electronic coherence in electron transfer.

Findings

Large-amplitude oscillations can occur in electronic occupation probabilities.

Initial system preparation critically affects the detection of electronic coherence.

Extended theoretical framework supports experimental investigation of coherence.

Abstract

The observability of electronic coherence in electron transfer reactions is discussed. We show that under appropriate circumstances large-amplitude oscillations can be found in the electronic occupation probabilities. The initial preparation of the system is of crucial importance for this effect, and we discuss conditions under which experiments detecting electronic coherence should be feasible. The Feynman-Vernon influence functional formalism is extended to examine more general and experimentally relevant initial preparations. Analytical expressions and path integral quantum dynamics simulations were developed to study the effects of various initial preparations on the observability of electronic coherence.