The use of multidimensional Franck-Condon simulations to assess model chemistries: a case study on phenol.
Multidimensional Franck-Condon simulations of the dispersed fluorescence spectra of phenol generated with geometries obtained from the highly correlated post-Hartree-Fock methods CASSCF, MRCI, and SACCI are presented. While the simulations based on CASSCF and MRCI optimized geometries are very similar to each other and fail to reproduce the experimentally measured intensities faithfully, the simulations obtained from SACCI optimized geometries are very close to the experimental spectra. The code developed for the multidimensional Franck-Condon simulations is described. It is shown that the integral storage problem common to the evaluation of multidimensional Franck-Condon integrals can be overcome by saving all quantities needed to disk. This strategy allows the code to run on computers with limited resources and is very well suited for application to molecules with a very large number of vibrational modes.
Pugliesi
Igor
I
Department of Chemistry, York Centre of Laser Spectroscopy, YCLS, The University of York, Heslington, York YO10 5DD, UK. igor.pugliesi@gmail.com
Müller-Dethlefs
Klaus
K