Two-Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two-Photon Absorption Spectrum of Reichardt's Dye
2013 (English)In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 14, no 16, 3731-3739 p.Article in journal (Refereed) Published
In this study, we report on the influence of solvent on the two-photon absorption (2PA) spectra of Reichardt's dye (RD). The measurement of 2PA cross-sections is performed for three solvents (chloroform, dimethyl formamide, and dimethyl sulfoxide) using the Z-scan technique. The key finding of this study is the observation that the cross-section, corresponding to the 2PA of the intramolecular charge-transfer state, diminishes substantially upon increasing the solvent polarity. To unravel the solvent dependence of the 2PA cross-section, the electronic structure of RD is determined using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach, in which polarization between the solute and solvent is taken into account by using a self-consistent scheme in the solvent polarization. The two-state approximation proves to be adequate for the studied system, and allowed the observed solvent-polarity-induced decrease of the 2PA cross-section to be related to the decrease of the transition moment and the increase in the excitation energy.
Place, publisher, year, edition, pages
2013. Vol. 14, no 16, 3731-3739 p.
absorption, charge transfer, density functional calculations, solvatochromism, solvent effects
Physical Sciences Chemical Sciences
IdentifiersURN: urn:nbn:se:kth:diva-134722DOI: 10.1002/cphc.201300695ISI: 000326311500017ScopusID: 2-s2.0-84887026428OAI: oai:DiVA.org:kth-134722DiVA: diva2:668324
QC 201311292013-11-292013-11-282013-11-29Bibliographically approved