Solving the Schrödinger equation of helium and its isoelectronic ions with the exponential integral (Ei) function in the free iterative complement interaction method.
We introduce here the exponential integral (Ei) function for variationally solving the Schrödinger equation of helium and its isoelectronic ions with the free iterative complement interaction (ICI) method. In our previous study [J. Chem. Phys., 2007, 127, 224104], we could calculate very accurate energies of these atoms by using the logarithmic function as the starting function of the free ICI calculation. The Ei function has a weak singularity at the origin, similarly to the logarithmic function, which is important for accurately describing the three-particle coalescence region. The logarithmic function, however, has a node and a maximum along the radial coordinate which may be physically meaningless. In contrast, the Ei function does not have such unphysical behaviors and so would provide an improvement over the logarithmic function. Actually, using the Ei function, instead of the logarithmic function, we obtained the energy, E= -2.903 724 377 034 119 598 311 159 245 194 404 446 696 924 865 a.u. for the helium ground state with 21 035 functions, which is a slight improvement over our previous result (the bold face shows the digits that are believed to have converged). This result supports the suggestion that the Ei function is better than the logarithmic function for describing the three-particle coalescence region.
Kurokawa
Yusaku I
YI
Quantum Chemistry Research Institute, JST, CREST, Kyodai Katsura Venture Plaza 106, Goryo Oohara 1-36, Nishikyo-ku, Kyoto, 615-8245, Japan.
Nakashima
Hiroyuki
H
Nakatsuji
Hiroshi
H
D003198:Computer Simulation; D006371:Helium / Q000737:chemistry*; D007477:Ions; D007526:Isoelectric Point; D011789:Quantum Theory; D013997:Time Factors
D007477:Ions; D006371:Helium