Abstract
Photoelectron circular dichroism (PECD) in the one-photon detachment of a model chiral anionic system is studied theoretically by the single center method. The computed chiral asymmetry, characterized by the dichroic parameter β1 of up to about ±3%, is in good accord with the first experimental observations of the effect in photodetachment of amino acid anions [P. Krüger and K. M. Weitzel, Angew. Chem., Int. Ed. 60, 17861 (2021)]. Our findings confirm a general assumption that the magnitude of PECD is governed by the ability of an outgoing photoelectron wave packet to accumulate characteristic chiral asymmetry from the short-range part of the molecular potential.
Highlights
The gas-phase laboratory-frame angular distribution of photoelectrons emitted from molecules, which are ionized by the absorption of one circularly polarized photon, is given by the total scitation.org/journal/jcp cross section σ, dichroic parameter β1, and anisotropy parameter β2 via22,23 dσd±Ω(θ) = 4σπ [1 ± β1P1(cos θ) − 12 β2P2(cos θ)]. (1)
Accurate description of the dichroic parameter β1, which is a subtractive quantity depending on differences between partial amplitudes and which is very sensitive to each and every particular detail of the molecular potential, requires reliable description of the electron continuum spectrum in molecules
We model the electronic potential of a chiral anionic system and apply a reliable theoretical approach to study its angle-resolved photodetachment by one-photon absorption
Summary
“±” stands for the positive or negative helicity of the light, PL are the Legendre polynomials, and θ is the angle between the direction of the propagation of the ionizing radiation and the direction of the emission of photoelectrons. The wave packet of an outgoing photoelectron accumulates this characteristic asymmetry by multiple scattering on the chiral molecular potential.
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