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Degenerate symmetry‐adapted perturbation theory. Convergence properties of perturbation expansions for excited states of H 2 + ion
Author(s) -
Chałasińaski Grezegorz,
Szalewicz Krzysztof
Publication year - 1980
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560180414
Subject(s) - degenerate energy levels , excited state , physics , atomic physics , hydrogen atom , perturbation (astronomy) , coulomb , quantum mechanics , perturbation theory (quantum mechanics) , ion , mathematical physics , quantum electrodynamics , group (periodic table) , electron
The degenerate Rayleigh‐Schrödinger ( RS ), Murrell–Shaw–Musher–Amos ( MSMA ), and Eisenschitz–London—Hirschfelder–van der Avoird ( EL–HAV ) perturbation theories are formulated and applied through high order to the interaction of a hydrogen atom with a proton for the excited 2 s σ g , 3 p σ u , 3 d σ g , and 4 f σ u states of the system. In contrast to the 1 s σ g and 2 p σ u states all the formalisms fail to provide a convergent series for any of the above states. However, numerical evidence is given that for sufficiently large internuclear separations the RS series is able to reproduce the Coulomb energy with an accuracy better than an arbitrary fraction of the exchange energy. Similarly the exchange energy can be reproduced by the sum of a few exchange corrections of the MSMA method. It has also been shown that both the MSMA and EL – HAV series can be continued analytically beyond the convergence radius by means of Padé approximants.