Accurate prediction of excited energy of rydberg states of OCIO and ab initio investigation of excited states of OCIO anion with a low energy

作者：Wei Zi Zhang; Li Bu Tong; Pan Qing Jiang; Zhang Hong Xing^*

来源：Chemical Journal of Chinese Universities, 2007, 28(11): 2183-2186.

• OCIO
• Complete active space self-consistent field (CASSCF)
• second-oder perturbation (CASM)
• ecited state
• Rydberg state

By using the complete active space self-consistent field (CASSCF) method with large atomic natural orbital (ANO-L) basis set, seven electronic states of the OCIO- anion were calculated. The optimized geometry of the ground state with ANO basis set agrees better with the experimental and previous theoretical values. Furthermore, the stable geometries of three singlet and three triplet excited states were obtained. Taking the further correlation effects into account, the second-order perturbation (CASPT2) calculations were carried out for the energetic calibration. Furthermore, the Rydberg states of the OCIO radical were investigated by using multiconfigurational CASPT2 (MS-CASPT2) theory under the basis set of ANO-L functions augmented with an adapted 1s1pld Rydberg functions that have specially been built for this study. Ten electronic excited states were found for the transition from 3b(1) electron into the Rydberg orbitals. The 3b(1)-> ns and 3b(1)-> np series agreed excellent with the experimental values, and the assignment of 3b(1)-> 3d series supported the results of Marston. Meanwhile, two and four Rydberg states were computed for the transition of 1a(2) and 5b(2) electron, respectively.

• 出版日期2007-11-10
• 单位黑龙江大学; 吉林大学