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Two-Photon Absorption Circular Dichroism: A new twist of nonlinear spectroscopy
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
2010 (English)In: CHEMISTRY-A EUROPEAN JOURNAL, ISSN 0947-6539, Vol. 16, no 11, 3504-3509 p.Article in journal (Refereed) Published
Abstract [en]

Most biological processes in nature are marked with a distinctive fingerprint: they only involveleft-handed molecules. This is one of the reasons why a thorough understanding of the chemical,physical and optical properties of chiral molecules and structures is of great significance for thescientific community. Chiroptical activity is commonly quantified in terms of one-photoncircular dichroism measurements. However, to uncover unusual chiroptical effects, polarizationdependent two-photon absorption becomes a useful spectroscopic alternative. The ability tocontrol at will the polarization of the photons that mediate the transition can increase thefundamental understanding regarding light-matter interactions in chiral systems. Herein wereport on the first experimental measurement of the two-photon absorption circular dichroismspectra and its theoretical support. The finding of new nonlinear fingerprints in chiral moleculesoffers new opportunities in the recognition and understanding of optically active systems inregions where CD present strong limitations.

Place, publisher, year, edition, pages
2010. Vol. 16, no 11, 3504-3509 p.
Keyword [en]
chirality; circular dichroism; two-photon absorption
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10339DOI: 10.1002/chem.200902286ISI: 000276058100027Scopus ID: 2-s2.0-77949283887OAI: oai:DiVA.org:kth-10339DiVA: diva2:216110
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2011-01-19Bibliographically 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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