Prediction of (1)P Rydberg energy levels of beryllium based on calculations with explicitly correlated Gaussians.
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).
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Sergiy
S
Bubin
Department of Chemistry and Biochemistry and Department of Physics, University of Arizona, Tucson, Arizona 85721, USA.
Ludwik
L
Adamowicz