Pachucki Krzysztof, Komasa Jacek
Institute of Theoretical Physics, Warsaw University, Hoza 69, 00-681 Warsaw, Poland.
J Chem Phys. 2006 Nov 28;125(20):204304. doi: 10.1063/1.2393226.
Variationally optimized exponentially correlated Gaussian functions are employed to obtain nonrelativistic wave functions of the lithium atom and its negative ion. The energy levels are computed by means of the expansion in powers of the fine-structure constant alpha. The first term of this expansion corresponds to the nonrelativistic energy. The higher order terms represent the relativistic and radiative corrections and are determined by some effective Hamiltonians. Highly accurate expectation values of singular operators entering these Hamiltonians are computed using a set of expectation value identities. The resulting electron affinity of lithium atom 4984.96(18) cm(-1) agrees very well with 4984.90(17) cm(-1) of the latest measurements.
采用变分优化的指数相关高斯函数来获得锂原子及其负离子的非相对论波函数。通过精细结构常数α的幂次展开来计算能级。该展开式的首项对应于非相对论能量。高阶项表示相对论和辐射修正,并由一些有效哈密顿量确定。使用一组期望值恒等式来计算进入这些哈密顿量的奇异算符的高精度期望值。所得锂原子的电子亲和能为4984.96(18) cm⁻¹,与最新测量值4984.90(17) cm⁻¹非常吻合。