Premium
Zero‐field splitting calculations based on semiempirical MR‐CI wave functions
Author(s) -
Mählmann Jürgen,
Klessinger Martin
Publication year - 2000
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/(sici)1097-461x(2000)77:1<446::aid-qua44>3.0.co;2-j
Subject(s) - wave function , hamiltonian (control theory) , diatomic molecule , atomic orbital , dipole , chemistry , quantum mechanics , slater type orbital , spin (aerodynamics) , gaussian , slater determinant , physics , atomic physics , computational chemistry , electron , molecule , molecular orbital theory , mathematics , mathematical optimization , thermodynamics
A method for computing the spin‐dipolar coupling tensor based on semiempirical MNDOC‐CI wave functions is described. To simulate the neglect of differential diatomic overlap (NDDO) approximation, Löwdin‐orthogonalized Gaussian‐type orbitals (GTOs) were used to evaluate the two electron integrals over the spin‐dependent Breit–Pauli Hamiltonian. Tests and applications of the method involve carbene, tetramethyleneethane, twisted ethylene, and ring‐opened oxirane biradical. The results provide a definition of the T x , T y , and T z triplet wave functions, the set of principal magnetic molecular axes, and the spin‐spin‐only values of the zero‐field splitting parameters D and E . © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 446–453, 2000