In this work, we extend the theoretical framework recently developed for the simulation of resonance Raman (RR) spectra of medium-to-large sized systems to its chiral counterpart, namely, resonance Raman optical activity (RROA). The theory is based on a time-dependent (TD) formulation, with the transition tensors obtained as half-Fourier transforms of the appropriate cross-correlation functions. The implementation has been kept as general as possible, supporting adiabatic and vertical models for the PES representation, both in Cartesian and internal coordinates, with the possible inclusion of Herzberg-Teller (HT) effects. Thanks to the integration of this TD-RROA procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects can be included in an effective way. The implementation is validated on one of the smallest chiral molecule (methyloxirane). Practical applications are illustrated with three medium-size organic molecules (naproxen-OCD3, quinidine and 2-Br-hexahelicene), whose simulated spectra are compared to the corresponding experimental data.

Time-Dependent Formulation of Resonance Raman Optical Activity Spectroscopy

Baiardi, Alberto;Bloino, Julien;Barone, Vincenzo
2018

Abstract

In this work, we extend the theoretical framework recently developed for the simulation of resonance Raman (RR) spectra of medium-to-large sized systems to its chiral counterpart, namely, resonance Raman optical activity (RROA). The theory is based on a time-dependent (TD) formulation, with the transition tensors obtained as half-Fourier transforms of the appropriate cross-correlation functions. The implementation has been kept as general as possible, supporting adiabatic and vertical models for the PES representation, both in Cartesian and internal coordinates, with the possible inclusion of Herzberg-Teller (HT) effects. Thanks to the integration of this TD-RROA procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects can be included in an effective way. The implementation is validated on one of the smallest chiral molecule (methyloxirane). Practical applications are illustrated with three medium-size organic molecules (naproxen-OCD3, quinidine and 2-Br-hexahelicene), whose simulated spectra are compared to the corresponding experimental data.
2018
Computer Science Applications1707 Computer Vision and Pattern Recognition; Physical and Theoretical Chemistry
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/78106
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