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Asymptotic behavior of two-electron expectation values in two-electron excited states
Authors:HE Montgomery  Jacob Katriel  KD Sen
Institution:1. Chemistry Program, Centre College, Danville, KY 40422, USA;2. Department of Chemistry, Technion - Israel Institute of Technology, Haifa, 32000, Israel;3. School of Chemistry, University of Hyderabad, Hyderabad-500 046, India
Abstract:Singly-excited states of the two-electron atom cease being bound when Z1 (from above), the outer orbital becoming infinitely diffuse. The asymptotic relationslimZ1?(Z?1)k(1sns)1,3S|r12k|(1sns)1,3S=(n?1)s(0)|rk|(n?1)s(0), where k=?1,1,2,3,?, are demonstrated to hold. Here, (n?1)s(0) is a hydrogenic s orbital with principal quantum number (n?1). New, more nuanced light is shed on the already challenged dogma that the Pauli principle keeps the electrons further apart in the triplet than in the corresponding singlet.
Keywords:Corresponding author    Two-electron atom  Two-electron expectation values  Critical charge  Asymptotic wave function
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