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Density functional electric response properties of molecules in Cartesian grid
Author(s) -
Ghosal Abhisek,
Mandal Tanmay,
Roy Amlan K.
Publication year - 2018
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.25708
Subject(s) - pseudopotential , polarizability , dipole , cartesian coordinate system , grid , diatomic molecule , hyperpolarizability , electric field , density functional theory , basis set , field (mathematics) , chemistry , physics , computational physics , molecule , computational chemistry , atomic physics , quantum mechanics , mathematics , geometry , pure mathematics
Within the finite‐field Kohn–Sham framework, static electric response properties of diatomic molecules are presented. The electronic energy, dipole moment ( μ ), static dipole polarizability ( α ), and first‐hyperpolarizability ( β ) are calculated through a pseudopotential‐DFT implementation in Cartesian coordinate grid, developed in our laboratory earlier. We engage the Labello–Ferreira–Kurtz (LFK) basis set; while four local and nonlocal exchange‐correlation (LDA, BLYP, PBE, and LBVWN) functionals have been adopted. A detailed analysis of grid convergence and its impact on obtained results is presented. In each case the electric field optimization was carefully monitored through a recently prescribed technique. For all three molecules (HCl, HBr, HI) considered, the agreement of all these quantities with widely successful and popular atom‐centered‐grid procedure, is excellent. To assess the efficacy and feasibility, companion calculations are performed for these on a representative molecule (HCl) at distorted geometries, far from equilibrium. Wherever possible, relevant comparison is made with available all‐electron data and experimental results. This demonstrates that Cartesian grid provides accurate, reliable results for such properties of many‐electron systems within pseudopotential representation.