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Title: General coalescence conditions for the exact wave functions. II. Higher-order relations for many-particle systems

We derived the necessary conditions that must be satisfied by the non-relativistic time-independent exact wave functions for many-particle systems at a two-particle coalescence (or cusp) point. Some simple conditions are known to be Kato's cusp condition (CC) and Rassolov and Chipman's CC. In a previous study, we derived an infinite number of necessary conditions that two-particle wave functions must satisfy at a coalescence point. In the present study, we extend these conditions to many-particle systems. They are called general coalescence conditions (GCCs), and Kato's CC and Rassolov and Chipman's CC are included as special conditions. GCCs can be applied not only to Coulombic systems but also to any system in which the interaction between two particles is represented in a power series of inter-particle distances. We confirmed the correctness of our derivation of the GCCs by applying the exact wave function of a harmonium in electron-electron and electron-nucleus coalescence situations. In addition, we applied the free complement (FC) wave functions of a helium atom to the GCCs to examine the accuracy of the FC wave function in the context of a coalescence situation.
Authors:
; ;  [1]
  1. Quantum Chemistry Research Institute, Kyodai Katsura Venture Plaza 107, Goryo Oohara 1-36, Nishikyo-ku, Kyoto 615-8245 (Japan)
Publication Date:
OSTI Identifier:
22304262
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 21; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; COALESCENCE; ELECTRONS; HELIUM; INTERACTIONS; PARTICLES; WAVE FUNCTIONS