US EPA

2709225 

Journal Article 

Theoretical modeling of UV-Vis absorption and emission spectra in liquid state systems including vibrational and conformational effects: the vertical transition approximation 

D'Alessandro, M; Aschi, M; Mazzuca, C; Palleschi, A; Amadei, A 

2013 

Yes 

Journal of Chemical Physics
ISSN: 0021-9606
EISSN: 1089-7690 

139 

11 

114102 

English 

24070274 

10.1063/1.4821003 

WOS:000324827800005 

https://www.scopus.com/inward/record.uri?eid=2-s2.0-84903362115&doi=10.1063%2f1.4821003&partnerID=40&md5=3d981dcaf5ae50833bf3d9ec3460acc6
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In this paper we describe in detail a general and efficient methodology, based on the perturbed matrix method and molecular dynamics simulations, to model UV-Vis absorption and emission spectra including vibrational and conformational effects. The basic approximation used is to consider all the chromophore atomic coordinates as semiclassical degrees of freedom, hence allowing the calculation of the complete spectral signal by using the electronic vertical transitions as obtained at each possible chromophore configuration, thus including the contributions of vibrations and conformational transitions into the spectrum. As shown for the model system utilized in this paper, solvated 1-phenyl-naphthalene, such an approximation can be rather accurate to reproduce the absorption and emission spectral line shape and properties when, as it often occurs, the vertical vibronic transition largely overlaps the other non-negligible vibronic transitions.