Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Department of Chemistry and Biochemistry and Department of Physics, University of Arizona, Tucson, Arizona 85721, USA.
J Chem Phys. 2014 Jan 14;140(2):024301. doi: 10.1063/1.4858275.
Benchmark variational calculations are performed for the seven lowest 1s(2)2s np ((1)P), n = 2...8, states of the beryllium atom. The calculations explicitly include the effect of finite mass of (9)Be nucleus and account perturbatively for the mass-velocity, Darwin, and spin-spin relativistic corrections. The wave functions of the states are expanded in terms of all-electron explicitly correlated Gaussian functions. Basis sets of up to 12,500 optimized Gaussians are used. The maximum discrepancy between the calculated nonrelativistic and experimental energies of 1s(2)2s np ((1)P) →1s(2)2s(2) ((1)S) transition is about 12 cm(-1). The inclusion of the relativistic corrections reduces the discrepancy to bellow 0.8 cm(-1).
对铍原子的七个最低 1s(2)2s np ((1)P)态，n = 2...8，进行了基准变分计算。计算明确包括了 (9)Be 核的有限质量的影响，并微扰地考虑了质量速度、达尔文和自旋-自旋相对论修正。这些态的波函数用全电子显式相关的高斯函数展开。使用多达 12500 个优化的高斯函数的基集。计算的非相对论能量与 1s(2)2s np ((1)P)→1s(2)2s(2) ((1)S)跃迁的实验能量之间的最大差异约为 12 cm(-1)。相对论修正的包含将差异减小到 0.8 cm(-1)以下。
