SFX Get it!(opens in a new window)|View at Publisher| Export | Download | Add to List | More... Journal of Chemical Theory and Computation Volume 12, Issue 6, 14 June 2016, Pages 2820-2833 Simulation of Vacuum UV Absorption and Electronic Circular Dichroism Spectra of Methyl Oxirane: The Role of Vibrational Effects (Article) Hodecker, M.ab, Biczysko, M.c , Dreuw, A.b, Barone, V.a a Scuola Normale Superiore, Piazza dei Cavalieri 7, Pisa, Italy b Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, Heidelberg, Germany c International Centre for Quantum and Molecular Structures, College of Sciences, Shanghai University, 99 Shangda Road, Shanghai, China View additional affiliations View references (103) Abstract Vibrationally resolved one-photon absorption and electronic circular dichroism spectra of (R)-methyl oxirane were calculated with different electronic and vibronic models selecting, through an analysis of the convergence of the results, the best compromise between reliability and computational cost. Linear-response TD-DFT/CAM-B3LYP/SNST electronic computations in conjunction with the simple vertical gradient vibronic model were chosen and employed for systematic comparison with the available experimental data. Remarkable agreement between simulated and experimental spectra was achieved for both one-photon absorption and circular dichroism concerning peak positions, relative intensities, and general spectral shapes considering the computational efficiency of the chosen theoretical approach. The significant improvement of the results with respect to smearing of vertical electronic transitions by phenomenological Gaussian functions and the possible inclusion of solvent effects by polarizable continuum models at a negligible additional cost paves the route toward the simulation and analysis of spectral shapes of complex molecular systems in their natural environment. © 2016 American Chemical Society.

Simulation of Vacuum UV Absorption and Electronic Circular Dichroism Spectra of Methyl Oxirane: The Role of Vibrational Effects

HODECKER, Manuel;BICZYSKO, MALGORZATA AGNIESZKA;BARONE, Vincenzo
2016

Abstract

SFX Get it!(opens in a new window)|View at Publisher| Export | Download | Add to List | More... Journal of Chemical Theory and Computation Volume 12, Issue 6, 14 June 2016, Pages 2820-2833 Simulation of Vacuum UV Absorption and Electronic Circular Dichroism Spectra of Methyl Oxirane: The Role of Vibrational Effects (Article) Hodecker, M.ab, Biczysko, M.c , Dreuw, A.b, Barone, V.a a Scuola Normale Superiore, Piazza dei Cavalieri 7, Pisa, Italy b Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, Heidelberg, Germany c International Centre for Quantum and Molecular Structures, College of Sciences, Shanghai University, 99 Shangda Road, Shanghai, China View additional affiliations View references (103) Abstract Vibrationally resolved one-photon absorption and electronic circular dichroism spectra of (R)-methyl oxirane were calculated with different electronic and vibronic models selecting, through an analysis of the convergence of the results, the best compromise between reliability and computational cost. Linear-response TD-DFT/CAM-B3LYP/SNST electronic computations in conjunction with the simple vertical gradient vibronic model were chosen and employed for systematic comparison with the available experimental data. Remarkable agreement between simulated and experimental spectra was achieved for both one-photon absorption and circular dichroism concerning peak positions, relative intensities, and general spectral shapes considering the computational efficiency of the chosen theoretical approach. The significant improvement of the results with respect to smearing of vertical electronic transitions by phenomenological Gaussian functions and the possible inclusion of solvent effects by polarizable continuum models at a negligible additional cost paves the route toward the simulation and analysis of spectral shapes of complex molecular systems in their natural environment. © 2016 American Chemical Society.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/63340
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