Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization
Goetz RE, Isaev TA, Nikoobakht B, Berger R, Koch CP (2017)
Publication Type: Journal article
Publication year: 2017
Journal
Book Volume: 146
Article Number: 024306
Journal Issue: 2
DOI: 10.1063/1.4973456
Abstract
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 two-photon 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 wavefunction 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.
Involved external institutions
Germany (DE)How to cite
APA:
Goetz, R.E., Isaev, T.A., Nikoobakht, B., Berger, R., & Koch, C.P. (2017). Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization. Journal of Chemical Physics, 146(2). https://doi.org/10.1063/1.4973456
MLA:
Goetz, R. E., et al. "Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization." Journal of Chemical Physics 146.2 (2017).
BibTeX: Download