A harmonic adiabatic approach in combination with density functional response theory for computing two photon vibronically resolved circular dichroism spectra of chiral molecules is presented. It includes both Franck-Condon and Herzberg-Teller contributions and it takes fully into account frequency changes and Duschinsky 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 a sign change in two-photon circular dichroism of a single excited electronic state of a conformer. The change survives after Boltzmann averaging, and it might be amenable to experimental verification. Interesting interference effects between Franck-Condon and Herzberg-Teller contributions are revealed and analyzed in detail. Results obtained within the more approximate and less computationally intensive linear coupling vibronic model are also given for comparison.
Theory for vibrationally resolved two-photon circular dichroism spectra. Application to (R)-(+)-3-methylcyclopentanone
Santoro F;Rizzo A;
2009
Abstract
A harmonic adiabatic approach in combination with density functional response theory for computing two photon vibronically resolved circular dichroism spectra of chiral molecules is presented. It includes both Franck-Condon and Herzberg-Teller contributions and it takes fully into account frequency changes and Duschinsky 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 a sign change in two-photon circular dichroism of a single excited electronic state of a conformer. The change survives after Boltzmann averaging, and it might be amenable to experimental verification. Interesting interference effects between Franck-Condon and Herzberg-Teller contributions are revealed and analyzed in detail. Results obtained within the more approximate and less computationally intensive linear coupling vibronic model are also given for comparison.File | Dimensione | Formato | |
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Descrizione: Theory for vibrationally resolved two-photon circular dichroism spectra. Application to (R)-(+)-3-methylcyclopentanone
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