Polarizable Embedding for Photoelectron Spectroscopy and Photoelectron Circular Dichroism in Solution: Core-Level Ionization of Aqueous Alanine

Abstract

We present a polarizable quantum-mechanics/molecular-mechanics formulation for the calculation of molecular photoionization observables in solution. The approach couples the static-exchange density-functional-theory treatment of bound and continuum electronic states with a fully atomistic polarizable embedding described with the fluctuating-charge force-field. The fluctuating charges are determined self-consistently with the ground-state quantum-mechanical density and are subsequently included in the static-exchange Hamiltonian to account for the outgoing electron. The numerical behavior of the coupled scheme is validated and applied to the X-ray photoelectron spectrum and photoelectron circular dichroism of zwitterionic L-alanine in aqueous solution, using an ensemble of configurations extracted from molecular dynamics. Calculated spectra reproduce experimental profiles remarkably well, demonstrating that atomistic solvent structure and environmental polarization must be treated together to reliably model photoelectron observables in aqueous solution.