Kirrander Adam, Child Mark S, Stolyarov Andrey V
Physical and Theoretical Chemistry Laboratory, Oxford University, Oxford OX1 3QZ, UK.
Phys Chem Chem Phys. 2006 Jan 14;8(2):247-55. doi: 10.1039/b511864f. Epub 2005 Oct 18.
Potential energy curves were evaluated for the ground and thirteen low-lying excited electronic states of the ArH molecule over a wide range of internuclear distances by the multi-reference averaged quadratic coupled cluster method. The ab initio energy differences and transition dipole moments were used to estimate Einstein emission coefficients, absorption oscillator strengths and radiative lifetimes. Diagonal and off-diagonal quantum defects, as functions of internuclear distance, were extracted from ab initio potentials of the lowest Rydberg states of the neutral ArH molecule by taking account of configuration interaction between Rydberg series converging to the ground and two electronic excited states of the ArH(+) cation. The derived quantum-defect functions were used to generate manifolds of higher excited Rydberg states. The agreement between experimental and calculated energies and radiative transition probabilities was found to be as good as or better than that obtained by earlier calculations.
通过多参考平均二次耦合簇方法，在广泛的核间距范围内评估了ArH分子基态和13个低激发电子态的势能曲线。利用从头算能量差和跃迁偶极矩来估计爱因斯坦发射系数、吸收振子强度和辐射寿命。通过考虑收敛到ArH(+)阳离子基态和两个电子激发态的里德堡系列之间的组态相互作用，从中性ArH分子最低里德堡态的从头算势中提取作为核间距函数的对角和非对角量子亏损。导出的量子亏损函数用于生成更高激发里德堡态的流形。发现实验和计算的能量以及辐射跃迁概率之间的一致性与早期计算的结果一样好或更好。
