# Characterization of the photoelectron circular dichroism of fixed-in-space molecules through an asymmetry of the ionic potential

## TL;DR

This paper explores how the asymmetry in the ionic potential of fixed-in-space molecules affects photoelectron emission patterns under circularly polarized light.

## Contribution

The paper introduces a new enantiosensitive dichroic characteristic of the ionic potential to explain PECD in fixed-in-space molecules.

## Key findings

- A forward-backward asymmetry in photoelectron emission can occur even in achiral fixed-in-space molecules.
- The PECD magnitude is linked to the asymmetry of the ionic potential in fixed molecular orientations.
- The proposed dichroic characteristic aligns with PECD landscapes for both chiral and achiral species.

## Abstract

Photoelectron circular dichroism (PECD) in the ionization of chiral molecules by circularly polarized radiation is a well-established tool for chiral recognition in the gas phase. The effect consists in a forward-backward asymmetry in angular emission distributions of photoelectrons with respect to the light propagation direction, which survives averaging over molecular orientations. Its magnitude is governed by the ability of the outgoing photoelectron to probe an asymmetry of the ionic potential by multiple scattering effects, and it can be significantly enhanced by fixing molecular orientation in space. Even achiral fixed-in-space molecules can exhibit such a forward-backward asymmetry in the photoemission. In the present work, we establish a qualitative correspondence between the PECD in one-photon ionization of fixed-in-space molecules and a degree of the asymmetry of their ionic potential. For this purpose, we introduce an enantiosensitive dichroic characteristic of the ionic potential, which describes a physical mechanism behind the forward-backward asymmetry in the photoemission from fixed-in-space molecules ionized by circularly polarized light. This characteristic, as a function of molecular orientation angles, can be compared to the respective PECD landscape. The present findings are exemplified by several applications to achiral and chiral species.