CASSCF and multireference CI with singles and doubles study of low-lying valence and Rydberg states of 2H-tetrazole.

Complete active space self-consistent field (CASSCF) and multireference CI with singles and doubles (MR-CISD) calculations [including extensivity corrections, at MR-CISD+Q and multireference averaged quadratic coupled cluster (MR-AQCC) levels] have been performed to characterize the low-lying valence and the Rydberg states of 2H-tetrazole. The highest level results (MR-AQCC/d'-aug'-cc-pVDZ) indicate the following ordering of the valence singlet excited states: S(1) (n-pi*), 6.06 eV; S(2) (n-pi*), 6.55 eV; S(3) (pi-pi*), 6.55 eV. The MR-CISD+Q/d'-aug'-cc-pVDZ results indicate the same ordering, but at slight higher energies: 6.16, 6.68, and 6.69 eV, respectively. According to our MR-CISD+Q/d'-aug'-cc-pVDZ results, the next two states are Rydberg states, at 7.69 eV (pi-3s) and 7.89 eV (n-3s). The calculated energies of these two states, as well as their proximity, are consistent with the conclusion reached by Palmer and Beveridge (Chem Phys 1987, 111, 249) that the first band of the photoelectron spectrum of 2H-tetrazole is likely to be associated to the first two ionizations processes (of pi and N lone pair electrons), at energies close to 11.3 eV. 2008 Wiley Periodicals, Inc.