Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization. / Goetz, R. E.; Isaev, T. A.; Nikoobakht, B.; Berger, R.; Koch, C. P.
In: Journal of Chemical Physics, Vol. 146, No. 2, 024306, 14.01.2017.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization
AU - Goetz, R. E.
AU - Isaev, T. A.
AU - Nikoobakht, B.
AU - Berger, R.
AU - Koch, C. P.
PY - 2017/1/14
Y1 - 2017/1/14
N2 - 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.
AB - 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.
KW - FUNCTIONAL RESPONSE THEORY
KW - PROBABILITY RATE CONSTANTS
KW - POLARIZATION DEPENDENCE
KW - 2-PHOTON ABSORPTION
KW - TRANSITION MOMENTS
KW - MASS-SPECTROMETRY
KW - BICYCLIC KETONES
KW - CROSS-SECTIONS
KW - PLANE-WAVE
KW - IONIZATION
U2 - 10.1063/1.4973456
DO - 10.1063/1.4973456
M3 - статья
VL - 146
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 2
M1 - 024306
ER -
ID: 13347764