Theory for Vibrationally Resolved Two-Photon Circular Dichroism Spectra: Application to(R)-(R)-(R)-(+)-3-Methylcyclopentanone
2009 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 113, no 16, 4198-4207 p.Article in journal (Refereed) Published
A harmonic adiabatic approach in combination with density functional response theory for computing twophotonvibronically resolved circular dichroism spectra of chiral molecules is presented. It includes bothFranck-Condon and Herzberg-Teller contributions and it takes fully into account frequency changes andDuschinsky effects. Model calculations have been performed for two dominant conformers of (R)-(+)-3-methylcyclopentanone in the gas phase. It is found that the Herzberg-Teller contribution can introduce asign change in two-photon circular dichroism of a single excited electronic state of a conformer. The changesurvives after Boltzmann averaging, and it might be amenable to experimental verification. Interestinginterference effects between Franck-Condon and Herzberg-Teller contributions are revealed and analyzedin detail. Results obtained within the more approximate and less computationally intensive linear couplingvibronic model are also given for comparison.
Place, publisher, year, edition, pages
2009. Vol. 113, no 16, 4198-4207 p.
chiral molecules; franck-condon; multiphoton absorption; exchange; density; liquid; spectroscopy; simulations; permanent; ethylene
IdentifiersURN: urn:nbn:se:kth:diva-10345DOI: 10.1021/jp8105925ISI: 000265383200061ScopusID: 2-s2.0-65749090654OAI: oai:DiVA.org:kth-10345DiVA: diva2:216138
QC 201007272009-05-072009-05-072010-12-06Bibliographically approved