基于完全相关高斯函数计算预测铍的 (1)P 里德堡能级。

Prediction of (1)P Rydberg energy levels of beryllium based on calculations with explicitly correlated Gaussians.

机构信息

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.

出版信息

J Chem Phys. 2014 Jan 14;140(2):024301. doi: 10.1063/1.4858275.

DOI:10.1063/1.4858275

PMID:24437871

Abstract

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).

摘要

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。