摘要
The potential energy curves （PECs） of four electronic states （X^1∑g＋, e^3△u, a3∑^-u, and d3Лg） of an As2 molecule are investigated employing the complete active space self-consistent field （CASSCF） method followed by the valence internally contracted multireference configuration interaction （MRCI） approach in conjunction with the correlation-consistent aug-cc- pV5Z basis set. The effect on PECs by the relativistic correction is taken into account. The way to consider the relativistic correction is to employ the second-order Douglas-Kroll Hamiltonian approximation. The correction is made at the level of a cc-pVSZ basis set. The PECs of the electronic states involved are extrapolated to the complete basis set limit. With the PECs, the spectroscopic parameters （Te, Re, ωe, ωeXe, ωeye, ae, βe, γe, and Be） of these electronic states are determined and compared in detail with those reported in the literature. Excellent agreement is found between the present results and the experimental data. The first 40 vibrational states are studied for each electronic state when the rotational quantum number J equals zero. In addition, the vibrational levels, inertial rotation and centrifugal distortion constants of d3Hg electronic state are reported which are in excellent agreement with the available measurements. Comparison with the experimental data shows that the present results are both reliable and accurate.
The potential energy curves （PECs） of four electronic states （X^1∑g＋, e^3△u, a3∑^-u, and d3Лg） of an As2 molecule are investigated employing the complete active space self-consistent field （CASSCF） method followed by the valence internally contracted multireference configuration interaction （MRCI） approach in conjunction with the correlation-consistent aug-cc- pV5Z basis set. The effect on PECs by the relativistic correction is taken into account. The way to consider the relativistic correction is to employ the second-order Douglas-Kroll Hamiltonian approximation. The correction is made at the level of a cc-pVSZ basis set. The PECs of the electronic states involved are extrapolated to the complete basis set limit. With the PECs, the spectroscopic parameters （Te, Re, ωe, ωeXe, ωeye, ae, βe, γe, and Be） of these electronic states are determined and compared in detail with those reported in the literature. Excellent agreement is found between the present results and the experimental data. The first 40 vibrational states are studied for each electronic state when the rotational quantum number J equals zero. In addition, the vibrational levels, inertial rotation and centrifugal distortion constants of d3Hg electronic state are reported which are in excellent agreement with the available measurements. Comparison with the experimental data shows that the present results are both reliable and accurate.
基金
supported by the National Natural Science Foundation of China (Grant No. 11247254)
the Program for Science and Technology Innovation Research Team in University of Henan Province, China (Grant No. 13IRTSTHN020)
the Program for Science and Technology of Henan Province, China (Grant Nos. 122300410331 and 12A140009)
