Ground-State Photoelectron Circular Dichroism of Methyl p-Tolyl Sulfoxide by Single-Photon Ionisation from a TableTop Source

被引：4

作者：

Waters, Max D. J. ^{[1
]}

Ladda, Nicolas ^{[2
]}

Senftleben, Arne ^{[2
]}

Svoboda, Vit ^{[1
,4
,5
]}

Belozertsev, Mikhail ^{[1
,3
]}

Baumert, Thomas ^{[2
]}

Woerner, Hans Jakob ^{[1
]}

机构：

[1] Swiss Fed Inst Technol, Lab Phys Chem, Vladimir Prelog Weg 2, CH-8093 Zurich, Switzerland

[2] Univ Kassel, Heinrich Plett Str 40, D-34132 Kassel, Germany

[3] Ludwig Maximilians Univ Munchen, Dept Chem, D-81377 Munich, Germany

[4] Univ Colorado, JILA, Boulder, CO 80309 USA

[5] NIST, Boulder, CO 80309 USA

来源：

CHEMPHYSCHEM | 2022年 / 23卷 / 24期

关键词：

chirality; high harmonic generation; photoelectron circular dichroism; methyl pare-tolyl sulfoxide; velocity map imaging; CHIRAL MOLECULES; ASYMMETRY; CHROMATOGRAPHY; RESONANCE; ENERGY;

D O I：

10.1002/cphc.202200575

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Single-photon ionisation of enantiopure methyl p-tolyl sulfoxide by circularly polarised light at 133 nm shows remarkably strong photoelectron circular dichroism (PECD), which has been measured in a velocity-map-imaging spectrometer. Both enantiomers were measured, each showing a PECD of a similar magnitude (ca. 25%). These experiments were carried out with a tabletop high-harmonic source with a photon energy of 9.3 eV, capable of ionising the electronic ground state of most organic and inorganic molecules. Ab-initio scattering calcula- tions provide a theoretical value of the expected chiral asymmetry parameter, and agree very well with the measured values once orbital mixing via configuration interaction in the cation is taken into account. This study demonstrates a simple photoionisation scheme that can be readily applied to study the time-resolved PECD of photochemical reactions and suggests a pronounced sensitivity of PECD to electronic configuration interaction in the cation.

引用

页数：7