Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule
Photoelectron circular dichroism (PECD), the forward–backward asymmetry of the photoelectron angular distribution when ionizing randomly oriented chiral molecules with circularly polarized light, is an established method to investigate chiral properties of molecules in their electronic ground state....
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| Format: | Article |
| Language: | English |
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AIP Publishing LLC and ACA
2023-11-01
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| Series: | Structural Dynamics |
| Online Access: | http://dx.doi.org/10.1063/4.0000213 |
| _version_ | 1797367014289833984 |
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| author | Marit R. Fiechter Vít Svoboda Hans Jakob Wörner |
| author_facet | Marit R. Fiechter Vít Svoboda Hans Jakob Wörner |
| author_sort | Marit R. Fiechter |
| collection | DOAJ |
| description | Photoelectron circular dichroism (PECD), the forward–backward asymmetry of the photoelectron angular distribution when ionizing randomly oriented chiral molecules with circularly polarized light, is an established method to investigate chiral properties of molecules in their electronic ground state. Here, we develop a computational strategy for predicting time-resolved PECD (TRPECD) of chemical reactions and demonstrate the method on the photodissociation of 1-iodo-2-methylbutane. Our approach combines multi-configurational quantum-chemical calculations of the relevant potential-energy surfaces of the neutral and singly ionized molecule with ab initio molecular-dynamics (AIMD) calculations. The PECD parameters along the AIMD trajectories are calculated with the aid of electron-molecule scattering calculations based on the Schwinger variational principle implemented in ePolyScat. Our calculations have been performed for two probe wavelengths (133 and 160 nm) accessible through low-order harmonic generation in gases. Our results show that the TRPECD is a highly sensitive probe of photochemical reaction dynamics. Most interestingly, the TRPECD is found to change sign multiple times along the photodissociation coordinate, in agreement with recent experiments on CHBrFI [Svoboda et al., “Femtosecond photoelectron circular dichroism of chemical reactions,” Sci. Adv. 8, eabq2811 (2022)]. The computational protocol introduced in the present work is general and readily applicable to other chiral photochemical processes. |
| first_indexed | 2024-03-08T17:11:49Z |
| format | Article |
| id | doaj.art-6e34e5aec61f40f0a053deeccb5ef423 |
| institution | Directory Open Access Journal |
| issn | 2329-7778 |
| language | English |
| last_indexed | 2024-03-08T17:11:49Z |
| publishDate | 2023-11-01 |
| publisher | AIP Publishing LLC and ACA |
| record_format | Article |
| series | Structural Dynamics |
| spelling | doaj.art-6e34e5aec61f40f0a053deeccb5ef4232024-01-03T19:59:31ZengAIP Publishing LLC and ACAStructural Dynamics2329-77782023-11-01106064103064103-910.1063/4.0000213Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral moleculeMarit R. Fiechter0Vít Svoboda1Hans Jakob Wörner2Laboratory of Physical Chemistry, ETH Zürich, 8093 Zurich, SwitzerlandLaboratory of Physical Chemistry, ETH Zürich, 8093 Zurich, SwitzerlandLaboratory of Physical Chemistry, ETH Zürich, 8093 Zurich, SwitzerlandPhotoelectron circular dichroism (PECD), the forward–backward asymmetry of the photoelectron angular distribution when ionizing randomly oriented chiral molecules with circularly polarized light, is an established method to investigate chiral properties of molecules in their electronic ground state. Here, we develop a computational strategy for predicting time-resolved PECD (TRPECD) of chemical reactions and demonstrate the method on the photodissociation of 1-iodo-2-methylbutane. Our approach combines multi-configurational quantum-chemical calculations of the relevant potential-energy surfaces of the neutral and singly ionized molecule with ab initio molecular-dynamics (AIMD) calculations. The PECD parameters along the AIMD trajectories are calculated with the aid of electron-molecule scattering calculations based on the Schwinger variational principle implemented in ePolyScat. Our calculations have been performed for two probe wavelengths (133 and 160 nm) accessible through low-order harmonic generation in gases. Our results show that the TRPECD is a highly sensitive probe of photochemical reaction dynamics. Most interestingly, the TRPECD is found to change sign multiple times along the photodissociation coordinate, in agreement with recent experiments on CHBrFI [Svoboda et al., “Femtosecond photoelectron circular dichroism of chemical reactions,” Sci. Adv. 8, eabq2811 (2022)]. The computational protocol introduced in the present work is general and readily applicable to other chiral photochemical processes.http://dx.doi.org/10.1063/4.0000213 |
| spellingShingle | Marit R. Fiechter Vít Svoboda Hans Jakob Wörner Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule Structural Dynamics |
| title | Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| title_full | Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| title_fullStr | Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| title_full_unstemmed | Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| title_short | Theoretical study of time-resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| title_sort | theoretical study of time resolved photoelectron circular dichroism in the photodissociation of a chiral molecule |
| url | http://dx.doi.org/10.1063/4.0000213 |
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