Title of article :
New expression for the expectation value integral for a confined helium atom
Author/Authors :
Pan، نويسنده , , Xiao-Yin and Sahni، نويسنده , , Viraht and Massa، نويسنده , , Lou and Sen، نويسنده , , K.D.، نويسنده ,
Issue Information :
روزنامه با شماره پیاپی سال 2011
Abstract :
A new expression for the expectation value integral of Hermitian operators for spherically symmetric states is derived in elliptical coordinates for the Helium atom confined in a cavity with infinite potential barrier walls. The expression is comprised of two components spanning different domains of space. For an atom in infinite space, with a wave function which satisfies Dirichlet boundary conditions, one of these terms is shown to vanish, but for a confined atom that same term cannot be neglected. In a variational calculation of the energy, for a helium atom confined by finite spheres of various radii, it is observed that the principal contribution is due to the first component, with the relative magnitude of the second component becoming smaller as the size of the cavity is increased. The expression derived is shown to be computationally faster than the conventionally employed expression for confined systems derived by ten Seldam-de Groot.
Keywords :
electron correlation , Dirichlet boundary condition , Confined helium , Hylleraas method
Journal title :
Computational and Theoretical Chemistry
Journal title :
Computational and Theoretical Chemistry