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Theory for Vibrationally Resolved Two-Photon Circular Dichroism Spectra: Application to(R)-(R)-(R)-(+)-3-Methylcyclopentanone
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0003-0007-0394
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
Abstract [en]

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.
Keyword [en]
chiral molecules; franck-condon; multiphoton absorption; exchange; density; liquid; spectroscopy; simulations; permanent; ethylene
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10345DOI: 10.1021/jp8105925ISI: 000265383200061Scopus ID: 2-s2.0-65749090654OAI: oai:DiVA.org:kth-10345DiVA: diva2:216138
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2010-12-06Bibliographically approved
In thesis
1. Theoretical Studies on Electronic and Vibrationally Resolved Multi-Photon Absorption and Dichroism
Open this publication in new window or tab >>Theoretical Studies on Electronic and Vibrationally Resolved Multi-Photon Absorption and Dichroism
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents time-dependent density functional theory studies on electronic and vibronically resolved linear and nonlinear optical absorption and dichroism spectra of organic molecules. Special attention has been paid to the influence of solvent environment and molecular vibrations on one-, two- and three-photon absorption and one- and two-photon circular dichroism.

It is found that dielectric medium as described by polarizable continuum model can enhance remarkably three-photon absorption cross section of a highly conjugated fluorene derivative, for which the simplified two-state model is shown to be largely inadequate. Origin-invariant density functional calculations on one- and two-photon circular dichroisms of a chiral molecule confirm that the recently developed CAMB3LYP functional performs better than the popular B3LYP functional for Rydberg-states. The first experimental measurement of TPCD spectra is performed on an axial chiral system in tetrahydrofunan, where the double L-scan technique is applied. Theoretical calculations well reproduce the experimental profiles when both the electron correlation and the solvent effect are taken into account. Vibronically resolved one- and two-photon absorption spectra of charge-transfer molecules have been obtained using a Linear Coupling model, where the 'borrowing mechanism' for the so-called Herzberg-Teller contribution is analyzed in detail. It is shown that Herzberg-Teller contribution can introduce a change of sign to the chiral responses of a molecule without the involvement of different electronic states, which has important consequences for the assignment of absolute configurations of chiral molecules. Adiabatic harmonic Franck-Condon model is also applied to simulate vibronically resolved one- and two-photon circular dichroism spectra of the same chiral system, where the sign-inversion and the interference between Franck-Condon and Herzberg-Teller contributions are also observed.

Place, publisher, year, edition, pages
Stockholm: KTH, 2009. xii, 67 p.
Series
Trita-BIO-Report, ISSN 1654-2312 ; 2009 : 09
Keyword
Multi-photon absorption and dichroism; Vibronically resolved spectroscopy
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10212 (URN)978-91-7415-277-7 (ISBN)
Public defence
2009-05-07, FA55, AlbaNova, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100727Available from: 2009-05-07 Created: 2009-04-12 Last updated: 2011-11-23Bibliographically approved

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