DOI

Photoelectron circular dichroism refers to the forward/backward asymmetry in the photoelectron angular distribution with respect to the propagation axis of circularly polarized light. It has recently been demonstrated in femtosecond multi-photon photoionization experiments with randomly oriented camphor and fenchone molecules [C. Lux et al., Angew. Chem., Int. Ed. 51, 4755 (2012) and C. S. Lehmann et al., J. Chem. Phys. 139, 234307 (2013)]. A theoretical framework describing this process as (2+ 1) resonantly enhanced multi-photon ionization is constructed, which consists of twophoton photoselection from randomly oriented molecules and successive one-photon ionization of the photoselected molecules. It combines perturbation theory for the light-matter interaction with ab initio calculations for the two-photon absorption and a single-center expansion of the photoelectron wave-function in terms of hydrogenic continuum functions. It is verified that the model correctly reproduces the basic symmetry behavior expected under exchange of handedness and light helicity. When applied to fenchone and camphor, semi-quantitative agreement with the experimental data is found, for which a sufficient d wave character of the electronically excited intermediate state is crucial. Published by AIP Publishing.

Original languageEnglish
Article number024306
Number of pages33
JournalJournal of Chemical Physics
Volume146
Issue number2
DOIs
StatePublished - 14 Jan 2017
Externally publishedYes

    Research areas

  • FUNCTIONAL RESPONSE THEORY, PROBABILITY RATE CONSTANTS, POLARIZATION DEPENDENCE, 2-PHOTON ABSORPTION, TRANSITION MOMENTS, MASS-SPECTROMETRY, BICYCLIC KETONES, CROSS-SECTIONS, PLANE-WAVE, IONIZATION

ID: 13347764