Theory of Non-Dichroic Enantio-Sensitive Chiroptical Spectroscopy

TL;DR

This paper introduces a novel enantio-sensitive chiroptical spectroscopy method based on non-dichroic contributions in photoelectron angular distributions, enabling robust, phase-insensitive detection of molecular chirality using two-color laser fields.

Contribution

It proposes a new NoDES protocol for chirality detection that is robust against phase variations and validates it through numerical simulations across multiple ionization regimes.

Findings

NoDES signal reaches about 1% of ionization yield.

The method is phase-robust and symmetry-protected.

Comparable in sensitivity to photoelectron circular dichroism.

Abstract

We show that the photoelectron angular distributions produced by elliptical and cross-polarized two-color laser fields interacting with randomly oriented chiral molecules decompose into four irreducible representations of the $D_{2h}$ point group. One of these ($A_u$) corresponds to a non-dichroic enantiosensitive (NoDES) contribution. This NoDES contribution has opposite sign for opposite enantiomers but remains invariant under reversal of the field ellipticity, enabling chirality detection that is robust against variations of the relative phase between orthogonal field components. We propose a protocol to isolate this component using only two velocity-map imaging projections and validate it through numerical simulations. Our calculations, performed in the two-photon resonantly-enhanced ionization, multi-photon, and strong-field ionization regimes with cross-polarized two-color fields show that the NoDES signal reaches about 1\% of the energy-resolved ionization yield, comparable to photoelectron circular dichroism and much larger than standard magnetic-dipole chiroptical effects. NoDES spectroscopy thus provides a symmetry-protected and phase-robust route to probe molecular chirality on the ultrafast time scale. The experimental confirmation of our theory is presented in the companion paper [L. Fede et al., arXiv:2512.19062 (2025)].