Tailoring Attosecond Charge Migration in Native Molecular Ions

TL;DR

This study explores how native charges in molecular ions influence attosecond charge migration, revealing that initial charge can either enhance or suppress electron dynamics depending on electron correlation strength.

Contribution

It provides the first theoretical analysis of attosecond charge migration in molecular ions, highlighting the impact of initial charge and electron correlation.

Findings

Presence of initial charge can degrade or improve charge migration.

Existence of dynamics correlates with electron correlation strength.

Results encourage further experimental and theoretical research.

Abstract

Attosecond chemistry involves developing strategies to manipulate electronic coherent waves in molecules, which can influence the outcome of photoinduced reactions. While recent progress in this field calls for investigations of increasingly complex isolated or embedded systems, theoretical predictions on attosecond charge migration have remained limited to native neutral species. Since molecules in nature often carry a native charge, there is potential biological and chemical interest in determining whether attosecond charge migration is affected by an additional charge. In this study, we employ high-level correlated methods to study purely electronic dynamics induced by hole-mixing in molecular ions. Our results, obtained for a series of neutral, protonated and deprotonated molecules, reveal that the likelihood of observing attosecond electron dynamics can either be degraded or improved by the presence of an initial charge, and that the existence of the dynamics is correlated with the strength of electron correlation. These findings will stimulate further experimental and theoretical investigations into this unexplored field of attosecond dynamics in molecular ions.