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Revisiting the generalized pseudospectral method: Radial expectation values, fine structure, and hyperfine splitting of confined atom
Author(s) -
Zhu Lin,
He Yu Ying,
Jiao Li Guang,
Wang Yuan Cheng,
Ho Yew Kam
Publication year - 2020
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.26245
Subject(s) - hydrogen atom , extrapolation , wave function , hyperfine structure , physics , radial function , schrödinger equation , excited state , computational physics , atomic physics , quantum mechanics , mathematical analysis , mathematics , group (periodic table)
This paper revisits the generalized pseudospectral (GPS) method on the calculation of various radial expectation values of atomic systems, especially on the spatially confined hydrogen atom and harmonic oscillator. As one of the collocation methods based on global functions, the powerfulness and robustness of the GPS method has been well established in solving the radial Schrödinger equation with high accuracy. However, in our recent work, it was found that the previous calculations based on the GPS method for the radial expectation values of confined systems show significant discrepancies with other theoretical methods. In this work we have tackled such a problem by tracing its source to the GPS method and found that the method itself may not be able to obtain the system wave function at the origin. Combined with an extrapolation method developed here, the GPS method can fully reproduce the radial quantities obtained by other theoretical methods, but with more flexibility, efficiency, and accuracy. We apply the GPS‐extrapolation method to investigate the relatievistic fine structure and hyperfine splitting of confined hydrogen atom in s ‐wave states where the zero‐point wave function dominates. Good agreement with previous predictions is obtained for confined hydrogen in low‐lying states, and benchmark results are obtained for high‐lying excited states. The perturbation treatment of the fine and hyperfine interactions is validated in the confining environment.