Toward Ab Initio Anharmonic Vibrational Circular Dichroism Spectra in the Condensed Phase.
The first implementation and calculation of anharmonic VCD rotational strengths for solvated systems is reported. Our approach, rooted in the polarizable continuum model (PCM) and in the second-order vibrational perturbation theory (VPT2), permits not only correction for anharmonicity in the signals associated with fundamental transitions but also calculation of rotational strengths of overtones and combination bands. This allows for a more physically consistent comparison between experiment and calculations together with the analysis of spectral regions dominated by anharmonic effects. The developed model is applied to a few test cases, and the computational outcomes are directly compared with experimental data.
†Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126 Pisa, Italy.|‡Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento, 35 I-56126 Pisa, Italy.
Chiara
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Cappelli
†Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126 Pisa, Italy.|¶CNR, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici, UOS di Pisa, Via G. Moruzzi, 1 I-56124 Pisa, Italy.
Julien
J
Bloino
†Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126 Pisa, Italy.
Filippo
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Lipparini
†Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126 Pisa, Italy.
Vincenzo
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Barone
chiroptical spectroscopy; polarizable continuum model; solvent effects; vibrational optical activity