Issue 30, 2008

Solving the Schrödinger equation of helium and its isoelectronic ions with the exponential integral (Ei) function in the free iterative complement interaction method

Abstract

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.

Graphical abstract: Solving the Schrödinger equation of helium and its isoelectronic ions with the exponential integral (Ei) function in the free iterative complement interaction method

Article information

Article type
Paper
Submitted
24 Apr 2008
Accepted
19 May 2008
First published
19 Jun 2008

Phys. Chem. Chem. Phys., 2008,10, 4486-4494

Solving the Schrödinger equation of helium and its isoelectronic ions with the exponential integral (Ei) function in the free iterative complement interaction method

Y. I. Kurokawa, H. Nakashima and H. Nakatsuji, Phys. Chem. Chem. Phys., 2008, 10, 4486 DOI: 10.1039/B806979B

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