Theoretical modeling of UV-Vis absorption and emission spectra in liquid state systems including vibrational and conformational effects: explicit treatment of the vibronic transitions.
Here, we extend a recently introduced theoretical-computational procedure [M. D'Alessandro, M. Aschi, C. Mazzuca, A. Palleschi, and A. Amadei, J. Chem. Phys. 139, 114102 (2013)] to include quantum vibrational transitions in modelling electronic spectra of atomic molecular systems in condensed phase. The method is based on the combination of Molecular Dynamics simulations and quantum chemical calculations within the Perturbed Matrix Method approach. The main aim of the presented approach is to reproduce as much as possible the spectral line shape which results from a subtle combination of environmental and intrinsic (chromophore) mechanical-dynamical features. As a case study, we were able to model the low energy UV-vis transitions of pyrene in liquid acetonitrile in good agreement with the experimental data.
Supercomputing Applications and Innovation, CINECA, Via dei Tizii, 6, 00185 Rome, Italy.
Marco
M
D'Abramo
Department of Physical and Chemical Sciences, University of Aquila, via Vetoio (Coppito 1), 67010 Aquila, Italy.
Massimiliano
M
Aschi
Dipartimento di Scienze e Tecnologie Chimiche Universita' di Roma, Tor Vergata, via della Ricerca Scientifica 1, I-00133 Roma, Italy.
Andrea
A
Amadei
D000097:Acetonitriles / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D044367:Phase Transition; D055585:Physical Phenomena; D011721:Pyrenes / Q000737:chemistry*; D011789:Quantum Theory; D014466:Ultraviolet Rays; D014732:Vibration
D000097:Acetonitriles; D011721:Pyrenes; C030984:pyrene; C032159:acetonitrile