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Theoretical Studies on Electronic and Vibrationally Resolved Multi-Photon Absorption and Dichroism
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512). (Department of Theoretical Chemistry)
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 [en]
Multi-photon absorption and dichroism; Vibronically resolved spectroscopy
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10212ISBN: 978-91-7415-277-7 (print)OAI: oai:DiVA.org:kth-10212DiVA: diva2:211255
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
List of papers
1. Solvent Effects on the Three-Photon Absorption of a Symmetric Charge-Transfer Molecule
Open this publication in new window or tab >>Solvent Effects on the Three-Photon Absorption of a Symmetric Charge-Transfer Molecule
2008 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 112, 4703-4710 p.Article in journal (Refereed) Published
Abstract [en]

We present a theoretical study of the solvent-induced three-photon absorption cross section of a highly conjugated fluorene derivative, performed using density functional (DFT) cubic response theory in combination with the polarizable continuum model. The applicability of the often used two-state model is examined by comparison against the full DFT response theory results. It is found that the simplified model performs poorly for the three-photon absorption properties of our symmetric charge-transfer molecule. The dielectric medium enhances the three-photon absorption cross section remarkably. The effects of solvent polarity and geometrical distortions have been carefully examined. A detailed comparison with experiment is presented.

Keyword
polarizable continuum model; 2-photon absorption; response functions; pulse-propagation; crystal-structure; fluorescence; excitation; stilbene; spectroscopy; solvation
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10337 (URN)10.1021/jp7107522 (DOI)000254883500033 ()2-s2.0-42949100757 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved
2. Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methyl-cyclopentanone
Open this publication in new window or tab >>Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methyl-cyclopentanone
2008 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 128, no 164312Article in journal (Refereed) Published
Abstract [en]

One- and two-photon circular dichroism spectra of R-(+)-3-methyl-cyclopentanone, a system that has been the subject of recent experimental studies of (2+1) resonance-enhanced multiphoton ionization circular dichroism, have been calculated with an origin-invariant density functional theory approximation in the region of the lowest electronic excited states, both for the gas phase and for a selection of solvents. A polarizable continuum model is used in the calculations performed on the solvated system. Two low-lying conformers are analyzed, and a comparison of the intensities and characteristic features is made with the corresponding two-photon absorption for each species, also for the Boltzmann-averaged spectra. The effect of the choice of geometry, basis set, and exchange-correlation functional is carefully analyzed. It is found that a density functional theory approach using the Coulomb attenuating method variant of Becke's three-parameter exchange and the Lee-Yang-Parr correlation functionals with correlation-consistent basis sets of double-zeta quality can reproduce the experimental electronic circular dichroism spectra very well. The features appearing in experiment are characterized in terms of molecular excitations, and the differences in the response of each state in the one- and two-photon processes are highlighted.

Keyword
polarizable continuum model; methyl-substituted cyclopentanones; molecular-orbital methods; nonequilibrium solvation; vacuum ultraviolet; optical-rotation; pure liquids; basis sets; gas-phase; solvent
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10338 (URN)10.1063/1.2907727 (DOI)000255456300033 ()2-s2.0-84962343567 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved
3. Two-Photon Absorption Circular Dichroism: A new twist of nonlinear spectroscopy
Open this publication in new window or tab >>Two-Photon Absorption Circular Dichroism: A new twist of nonlinear spectroscopy
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.

Keyword
chirality; circular dichroism; two-photon absorption
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10339 (URN)10.1002/chem.200902286 (DOI)000276058100027 ()2-s2.0-77949283887 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2011-01-19Bibliographically approved
4. Theoretical modeling of two-photon circulardichroism of R-(+)-1,1’-bi-2-naphthol
Open this publication in new window or tab >>Theoretical modeling of two-photon circulardichroism of R-(+)-1,1’-bi-2-naphthol
(English)Article in journal (Refereed) Submitted
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10340 (URN)
Note
QS 20120327Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2012-03-27Bibliographically approved
5. Vibronic induced one- and two-photon absorption in a charge-transfer stilbene derivate
Open this publication in new window or tab >>Vibronic induced one- and two-photon absorption in a charge-transfer stilbene derivate
2007 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 126, no 244509Article in journal (Refereed) Published
Abstract [en]

Both the electronic and the vibronic contributions to one- and two-photon absorption of a D-pi-D charge-transfer molecule (4-dimethylamino-4(')-methyl-trans stilbene) are studied by means of density functional response theory combined with a linear coupling model. Vibronic profiles of the first four excited states are fully explored. The dominating vibrational modes for both Franck-Condon and Herzberg-Teller contributions are identified. The Franck-Condon contribution dominates the spectra of first, second, and fourth excited states. The Herzberg-Teller contribution is on the other hand of comparable size for the third excited state, where its inclusion leads to a blueshift with respect to the vertical transition. A similar vibronic coupling behavior is found for both one- and two-photon absorptions

Keyword
density-functional theory; molecular-structure; crystal-structure; benzene; chromophores; spectrum; fluorescence; profiles; band
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10341 (URN)10.1063/1.2745794 (DOI)000247625800042 ()2-s2.0-34547291966 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved
6. Vibronically induced shift between one- and two-photon absorption spectra
Open this publication in new window or tab >>Vibronically induced shift between one- and two-photon absorption spectra
(English)Manuscript (Other academic)
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10342 (URN)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2010-07-27Bibliographically approved
7. Vibronically-induced change in the chiral response of molecules revealed by electronic circular dichroism spectroscopy
Open this publication in new window or tab >>Vibronically-induced change in the chiral response of molecules revealed by electronic circular dichroism spectroscopy
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.

Keyword
optical-activity; 2-photon absorption; exchange; density; approximation; simulations
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10343 (URN)10.1016/j.cplett.2008.09.013 (DOI)000260259000004 ()2-s2.0-53549119932 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved
8. Vibronically Resolved Electronic Circular Dichroism Spectra of (R)-(+)-3-Methylcyclopentanone: A Theoretical Study
Open this publication in new window or tab >>Vibronically Resolved Electronic Circular Dichroism Spectra of (R)-(+)-3-Methylcyclopentanone: A Theoretical Study
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.

Keyword
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:nbn:se:kth:diva-10344 (URN)10.1021/jp8064695 (DOI)000261218100015 ()2-s2.0-57949095711 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved
9. Theory for Vibrationally Resolved Two-Photon Circular Dichroism Spectra: Application to(R)-(R)-(R)-(+)-3-Methylcyclopentanone
Open this publication in new window or tab >>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
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.

Keyword
chiral molecules; franck-condon; multiphoton absorption; exchange; density; liquid; spectroscopy; simulations; permanent; ethylene
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-10345 (URN)10.1021/jp8105925 (DOI)000265383200061 ()2-s2.0-65749090654 (Scopus ID)
Note
QC 20100727Available from: 2009-05-07 Created: 2009-05-07 Last updated: 2017-12-13Bibliographically approved

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