Wydział Chemii

Julien Bloino

Małgorzata Biczysko

Orlando Crescenzi

Vincenzo Barone

2008

Journal of Chemical Physics

128

244105/1-244105/15

10.1063/1.2943140

Naukowa

Angielski

Artykuł

A new general and effective procedure to compute Franck–Condon spectra from first principles is exploited to elucidate the subtle features of the vibrationally resolved optical spectra of anisole. Methods based on the density functional theory and its time-dependent extension for electronic excited states [B3LYP/ 6-311+ G(d,p) and TD-B3LYP/ 6-311+ G(d,p)] have been applied to geometry optimizations and harmonic frequency calculations. Perturbative anharmonic frequencies [J. Chem. Phys. 122, 014108 (2005)] have been calculated for the ground state, and the Duschinsky matrix elements have been used to evaluate the corresponding anharmonic corrections for the first excited electronic state. The relative energetics of both electronic states has been refined by single point calculations at the coupled clusters (CC) level with the aug-cc-pVDZ basis set. Theoretical spectra have been evaluated using a new optimized implementation for the effective computation of Franck–Condon factors. The remarkable agreement between theoretical and experimental spectra allowed for revision of some assignments of fundamental vibrations in the S₁ state of anisole.

http://dx.doi.org/10.1063/1.2943140

https://www.aip.org/