The vertical electronic spectrum of the thiophene molecule is investigated by means of second and third order multireference perturbation theory (NEVPT). Single-state and quasi-degenerate NEVPT calculations of more than 25 singlet excited states have been performed. The study is addressed to the theoretical characterization of the four lowest-energy pi->pi* valence states, as well as the 3s, 3p and 3d Rydberg states. In addition, the excitation energies of two pi->sigma* and n->pi* valence states are also reported. For almost all the excited states, coupled cluster calculations (CCSD and CCSDR(3)) have been also carried out, using the same geometry and basis set used for the NEVPT ones, in order to make the comparison between the results of the two methods meaningful. A remarkable accordance between the NEVPT and CC excitation energies is found. The present results, over all, confirm the experimental assignments but, above all, represent an important contribution to the assignments of some low-energy pi->sigma* states, valence and Rydberg, for which a firm interpretation is not available in the literature.
A multireference perturbation theory study on the vertical electronic spectrum of thiophene
PASTORE, Mariachiara;ANGELI, Celestino;CIMIRAGLIA, Renzo
2007
Abstract
The vertical electronic spectrum of the thiophene molecule is investigated by means of second and third order multireference perturbation theory (NEVPT). Single-state and quasi-degenerate NEVPT calculations of more than 25 singlet excited states have been performed. The study is addressed to the theoretical characterization of the four lowest-energy pi->pi* valence states, as well as the 3s, 3p and 3d Rydberg states. In addition, the excitation energies of two pi->sigma* and n->pi* valence states are also reported. For almost all the excited states, coupled cluster calculations (CCSD and CCSDR(3)) have been also carried out, using the same geometry and basis set used for the NEVPT ones, in order to make the comparison between the results of the two methods meaningful. A remarkable accordance between the NEVPT and CC excitation energies is found. The present results, over all, confirm the experimental assignments but, above all, represent an important contribution to the assignments of some low-energy pi->sigma* states, valence and Rydberg, for which a firm interpretation is not available in the literature.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
