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Solvent effects on the vibronic one-photon absorption profiles of dioxaborine heterocycles
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
Department of Chemistry, University of Arizona.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
Department of Chemistry, University of Arizona.
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2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 123, no 19, 194311-1-194311-7 p.Article in journal (Refereed) Published
Abstract [en]

The vibronic profiles of one-photon absorption spectra of dioxaborine heterocycles in gas phase and solution have been calculated at the Hartree-Fock and density-functional-theory levels. The polarizable continuum model has been applied to simulate the solvent effect, while the linear coupling model is used to compute the Franck-Condon and Herzberg-Teller contributions. It is found that a good agreement between theory and experiment can be achieved when the solvent effect and electron correlation are taken into account simultaneously. For the first excited charge-transfer state, the maximum of its Herzberg-Teller profile is blueshifted from that of the Franck-Condon profile. The shifted energy is found to be around 0.2 eV, which agrees well with the measured energy difference between two- and one-photon absorptions of the first excited state.

Place, publisher, year, edition, pages
2005. Vol. 123, no 19, 194311-1-194311-7 p.
Keyword [en]
Charge transfer; Energy absorption; Mathematical models; Molecular vibrations; Organic solvents; Probability density function; Dioxaborine; Hartree-Fock levels; Photon absorption; Solvent effects; Boron compounds
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-6975DOI: 10.1063/1.2121590ISI: 000233353200023Scopus ID: 2-s2.0-27744587300OAI: oai:DiVA.org:kth-6975DiVA: diva2:11840
Note
QC 20100820Available from: 2007-04-16 Created: 2007-04-16 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Theoretical Design of Molecular Photonic Materials
Open this publication in new window or tab >>Theoretical Design of Molecular Photonic Materials
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis presents a theoretical study on optical properties of molecular materials. Special emphasis has been put on the influence of solvent environment, nuclear vibrations, and aggregation effects on molecular properties like linear and nonlinear polarizabilities, one- and two-photon absorption probabilities. All calculations have been performed by means of time independent and dependent quantum chemical methods at the Hartree-Fock and density functional theory levels. Solvation models that include both long range and short range interactions have been employed for calculations of optical properties of molecules in solutions. Pure vibrational and zero-point vibrationally averaged contributions have been taken into account for linear and nonlinear polarizabilities. The linear coupling model is applied to simulate vibronic profiles of optical absorption spectra. The computational strategies described in this thesis are very useful for the design of efficient molecular photonic materials.

More specifically, the nonmonotonic behavior of the solvatochromic shifts and the first hyperpolarizability of para-nitroaniline (pNA) with respect to the polarity of the solvents have been theoretically confirmed for the first time. The significant contributions of the hydrogen bonding on the electronic structures of pNA are revealed. Vibrational contributions to the linear and nonlinear polarizabilities of methanol, ethanol and propanol have been calculated both at the static limit and in dynamic optical processes. The importance of vibrational contributions to certain nonlinear optical processes have been demonstrated. A series of end-capped triply branched dendritic chromophores have been studied with the result that their second order nonlinear optical properties are found strongly dependent on the mutual orientations of the three chromophores, numbers of caps and the conjugation length of the chromophores. Several possible mechanisms for the origin of the Q-band splitting of aluminum phthalocyanine chloride have been examined. Calculated vibronic one-photon absorption profiles of two molecular systems are found to be in very good agreement with the corresponding experiments, allowing to provide proper assignments for different spectral features. Furthermore, effects of vibronic coupling in the nonradiative decay processes have been considered which helps to understand the aggregation enhanced luminescence of silole molecules. The study of molecular aggregation effects on two-photon absorption cross sections of octupolar molecules has highlighted the need to use a hybrid method that combines density functional response theory and molecular dynamics simulations for the design of molecular materials.

Place, publisher, year, edition, pages
Stockholm: KTH, 2007. 52 p.
Series
Trita-TEC-PHD, ISSN 1653-4468
Keyword
Optical property, Molecular material, Solvent environment, Nuclear vibrations, Aggregation effect
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-4333 (URN)978-91-7178-619-7 (ISBN)
Public defence
2007-04-27, FA32, Roslagstullsbacken 21, AlbaNova University Center, Stockholm, 14:00
Opponent
Supervisors
Note
QC 20100820Available from: 2007-04-16 Created: 2007-04-16 Last updated: 2010-08-20Bibliographically approved

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