Distinctive Onset of Electron Correlation in Molecular Tautomers

TL;DR

This study examines how the initial electron response time after ionization varies with molecular structure and symmetry, revealing differences in ultrafast charge migration in tautomeric systems.

Contribution

It introduces an ab initio multielectron wave-packet propagation approach to analyze the onset of electron correlation in molecular tautomers.

Findings

Electron response time varies with molecular structure and orbital symmetry.

Distinct temporal signatures of charge migration are observed in tautomeric hydrogen systems.

The onset of electron correlation is sensitive to molecular complexity.

Abstract

We investigate the attosecond response of the electronic cloud of a molecular system to an outer-valence ionization. The time needed for the remaining electrons to respond to a sudden perturbation in the electronic structure of the molecule is a measure of the degree of electron correlation. Using the ab initio multielectron wave-packet propagation method, we show that this response time can be sensitive to the molecular structure and the symmetry of the ionized molecular orbital. Our analysis revealed differences in the temporal signatures of ultrafast charge migration processes in the context of tautomeric hydrogen in multinuclear systems, and the relevance of distinctive onset of electron correlation within the overall molecular complexity.