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Vibronically Resolved Electronic Circular Dichroism Spectra of (R)-(+)-3-Methylcyclopentanone: A Theoretical Study
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, 12401-12411 p.Article in journal (Refereed) Published
Abstract [en]

The vibrationally resolved electronic circular dichroism (ECD) spectra of the two dominant conformers of (R)-(+)-3-methylcyclopentanone in gas phase are computed by density functional response theory, with a full account of Franck-Condon and Herzberg-Teller vibrational contributions at the harmonic level. Proper inclusion of the latter contributions was made possible by the recent implementation of effective-scaling computations of vibrational overlaps and of analytical gradients of time dependent DFT. The Coulomb-attenuated Becke three parameters Lee-Yang-Parr (CAM-B3LYP) functional reproduces both the position and the intensity of the experimental peaks, providing a remarkable improvement over the spectra obtained with the popular hybrid B3LYP functional, and allowing a confident assignment of the CD fine vibrational structure. Franck-Condon and Herzberg-Teller contributions are discussed in detail. The Computed decrease of the CID intensity in the gas phase upon increase of the temperature of the sample follows the trend observed experimentally in different solvents.

Place, publisher, year, edition, pages
2008. Vol. 112, 12401-12411 p.
Keyword [en]
franck-condon principle; substituted cyclopentanones; polyatomic-molecules; 2-photon absorption; vacuum ultraviolet; optical-activity; herzberg-teller; exchange; density; solvent
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10344DOI: 10.1021/jp8064695ISI: 000261218100015Scopus ID: 2-s2.0-57949095711OAI: oai:DiVA.org:kth-10344DiVA: diva2:216136
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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