The effect of the pi-electron delocalization curvature on the two-photon circular dichroism of molecules with axial chirality
| Autor: | Rémy Passier, Antonio Rizzo, Na Lin, Florencio E. Hernandez, Carlos Diaz, Carlos Toro |
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| Jazyk: | angličtina |
| Rok vydání: | 2012 |
| Předmět: |
Circular dichroism
Chemistry Transition dipole moment biaryl derivatives Molecular physics Polarizable continuum model magnetic transition dipole moment Delocalized electron nonlinear rotatory strength Computational chemistry Axial chirality circular polarization General Materials Science Density functional theory Physical and Theoretical Chemistry molecular currents Circular polarization Basis set |
| Zdroj: | The journal of physical chemistry letters 3 (2012): 1808–1813. doi:10.1021/jz300577e info:cnr-pdr/source/autori:Diaz, C; Lin, N; Toro, C; Passier, R; Rizzo, A; Hernandez, F E/titolo:The effect of the pi-electron delocalization curvature on the two-photon circular dichroism of molecules with axial chirality/doi:10.1021%2Fjz300577e/rivista:The journal of physical chemistry letters/anno:2012/pagina_da:1808/pagina_a:1813/intervallo_pagine:1808–1813/volume:3 |
| DOI: | 10.1021/jz300577e |
| Popis: | Herein we report on the theoretical-experimental study of the effect of curvature of the π-electron delocalization on the two-photon circular dichroism (TPCD) of a family of optically active biaryl derivatives (S-BINOL, S-VANOL, and S-VAPOL). The comparative analysis of the influence of the different transition moments to their corresponding TPCD rotatory strength reveals an enhanced contribution of the magnetic transition dipole moment on VAPOL. This effect is hereby attributed to the additional twist in the π-electron delocalization on this compound. TPCD measurements were done using the double L-scan technique in the picosecond regime. Theoretical calculations were completed using modern analytical response theory, within a time-dependent density functional theory (TD-DFT) approach, at both, B3LYP and CAM-B3LYP levels, with the aug-cc-pVDZ basis set for S-BINOL and S-VANOL, and 6-31G* for S-VAPOL. Solvent effects were included by means of the polarizable continuum model (PCM) in CH2Cl2. |
| Databáze: | OpenAIRE |
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