A theoretical study of electronic spectra in the linear cationic chains NC2n+1N+(n=1-6)

作者：Zhao Yuan; Guo Jia; Zhang Jinglai^*

来源：Chemical Physics, 2011, 386(1-3): 23-28.

DOI：10.1016/j.chemphys.2011.05.013

• NC2n+1N+
• Electronic spectra
• Excited state
• Ab initio study

The B3LYP, CAM-B3LYP, and RCCSD(T) theories have been used to calculate the ground state equilibrium geometries of the linear cationic chains NC2n+1N+ (n = 1-6). Compared with the system NC2nN+, the odd-n cationic chains are more susceptible to fragmentation than the even-n cationic chains. The complete active space self-consistent-field method has been utilized to determine the stationary structure of the ground state (X-2 Pi(g/u)) and first excited state (1(2)Pi(u/g)). The complete active space second-order perturbation theory has been used to compute the vertical excitation energies for the dipole-allowed (1, 2, 3)(2)Pi(u/g) <- X-2 Pi(g/u) transitions as well as the dipole-forbidden 1(2)Phi u/g <- X-2 Pi(g/u) transitions. The calculated transition energies of 1(2)Pi(u/g) <- X-2 Pi(g/u) in the gas phase are 2.61, 2.37, 2.07, 1.88, 1.64, and 1.34 eV, respectively, which accord well with the available experimental values. Moreover, the absorption spectra of 2(2)Pi(u/g) <- X-2 Pi(u/g) may be detected more easily among the selected four transitions.

• 出版日期2011-7-28
• 单位河南大学