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2024-06-03Subject
530 Physics 540 Chemistry ReihenentwicklungOptimierungsproblemPhotoelektronenspektroskopieZirkulardichroismusChiralität <Chemie>FotoionisationMetadata
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Optimal photoelectron circular dichroism of a model chiral system
Abstract
We optimize the internuclear geometry and electronic structure of a model chiral system to achieve a maximal photoelectron circular dichroism (PECD) in its one-photon ionization by circularly polarized light. The electronic structure calculations are performed by the single center method, while the optimization is done using quantum alchemy employing a Taylor series expansion. Thereby, the effect of bond lengths and uncompensated charge distributions on the chiral response of the model is investigated theoretically in some detail. It is demonstrated that manipulating a chiral asymmetry of the ionic potential may enhance the dichroic parameter (i.e., the PECD) of the randomly oriented model system well beyond β1 = 25%. Furthermore, we demonstrate that quantum alchemy is applicable to PECD despite the unusually strong coupling of spatial and electronic degrees of freedom and discuss the relative impact of the individual degrees of freedom in this model system. We define the necessary conditions for the computational design of PECD for real (non-model) chiral molecules using our approach.
Citation
In: The Journal of Chemical Physics Volume 160 / Issue 21 (2024-06-03) eissn:1089-7690Sponsorship
Gefördert im Rahmen eines Open-Access-Transformationsvertrags mit dem VerlagCitation
@article{doi:10.17170/kobra-2024061110327,
author={von Rudorff, Guido Falk and Artemyev, Anton N. and Lagutin, Boris M. and Demekhin, Philipp V.},
title={Optimal photoelectron circular dichroism of a model chiral system},
journal={The Journal of Chemical Physics},
year={2024}
}
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2024-06-21T10:16:21Z 2024-06-21T10:16:21Z 2024-06-03 doi:10.17170/kobra-2024061110327 http://hdl.handle.net/123456789/15867 Gefördert im Rahmen eines Open-Access-Transformationsvertrags mit dem Verlag eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ series expansion optimization problems circular dichroism spectroscopy chirality chirality control photoionization 530 540 Optimal photoelectron circular dichroism of a model chiral system Aufsatz We optimize the internuclear geometry and electronic structure of a model chiral system to achieve a maximal photoelectron circular dichroism (PECD) in its one-photon ionization by circularly polarized light. The electronic structure calculations are performed by the single center method, while the optimization is done using quantum alchemy employing a Taylor series expansion. Thereby, the effect of bond lengths and uncompensated charge distributions on the chiral response of the model is investigated theoretically in some detail. It is demonstrated that manipulating a chiral asymmetry of the ionic potential may enhance the dichroic parameter (i.e., the PECD) of the randomly oriented model system well beyond β1 = 25%. Furthermore, we demonstrate that quantum alchemy is applicable to PECD despite the unusually strong coupling of spatial and electronic degrees of freedom and discuss the relative impact of the individual degrees of freedom in this model system. We define the necessary conditions for the computational design of PECD for real (non-model) chiral molecules using our approach. open access von Rudorff, Guido Falk Artemyev, Anton N. Lagutin, Boris M. Demekhin, Philipp V. doi:10.1063/5.0209161 Reihenentwicklung Optimierungsproblem Photoelektronenspektroskopie Zirkulardichroismus Chiralität <Chemie> Fotoionisation publishedVersion eissn:1089-7690 Issue 21 The Journal of Chemical Physics Volume 160 false 214301
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