Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Vibronically-induced change in the chiral response of molecules revealed by electronic circular dichroism spectroscopy
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0003-0007-0394
2008 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 464, 144-149 p.Article in journal (Refereed) Published
Abstract [en]

A computational study of the vibronically resolved electronic circular dichroism (ECD) spectra of R-(+)- 3-methyl-cyclopentanone, including both Franck-Condon and Herzberg-Teller contributions, shows how the latter can introduce a change of sign on the chiral response of an electronic excited state. This sign inversion within the vibronically resolved electronic band, which can be interpreted as a change of the chirality of the system, has in principle important consequences in comparisons of theoretical and experimental ECD spectra employed for the assignment of absolute configurations.

Place, publisher, year, edition, pages
2008. Vol. 464, 144-149 p.
Keyword [en]
optical-activity; 2-photon absorption; exchange; density; approximation; simulations
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10343DOI: 10.1016/j.cplett.2008.09.013ISI: 000260259000004Scopus ID: 2-s2.0-53549119932OAI: oai:DiVA.org:kth-10343DiVA: diva2:216132
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically 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

Open Access in DiVA

No full text

Other links

Publisher's full textScopushttp://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TFN-4TF2J58-1&_user=4478132&_rdoc=1&_fmt=&_orig=search&_sort=d&view=c&_acct=C000034958&_version=1&_urlVersion=0&_userid=4478132&md5=a74c11cbe8b310ea1e5ad28a3173a421

Authority records BETA

Luo, Yi

Search in DiVA

By author/editor
Lin, NaLuo, Yi
By organisation
Theoretical Chemistry
In the same journal
Chemical Physics Letters
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 43 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf