Wydział Chemii

Manuel Hodecker

Małgorzata Biczysko

Andreas Dreuw

Vincenzo Barone

2016

Journal of Chemical Theory and Computation

12

2820-2833

10.1021/acs.jctc.6b00121

Naukowa

Angielski

Artykuł

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 theresults with respect to smearing of vertical electronic transitions by phenomenological Gaussian functions and the possibleinclusion 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.

http://dx.doi.org/10.1021/acs.jctc.6b00121

https://www.acs.org/content/acs/en.html