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The Fock Matrix Analysis for Atomic Orbitals in Molecular Orbitals II. The Electronic Structure of N 2 Molecules
Author(s) -
Hsu WenYi,
Lee HsingYi,
Wang ShaoPin,
Chang TseChiang
Publication year - 2008
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200800015
Subject(s) - natural bond orbital , linear combination of atomic orbitals , molecular orbital theory , molecular orbital , localized molecular orbitals , chemistry , slater type orbital , valence bond theory , molecular orbital diagram , orbital hybridisation , diradical , atomic orbital , complete active space , cubic harmonic , electron configuration , atomic physics , molecular physics , computational chemistry , molecule , physics , electron , density functional theory , quantum mechanics , organic chemistry , singlet state , excited state
Weinhold's natural hybrid orbitals can be chosen as the molecular adapted atomic orbitals to build the canonical molecular orbitals of N 2 molecules. The molecular Fock matrix expanded in the natural hybrid orbitals can reveal deeper insight of the electronic structure and reaction of the N 2 molecule. For example, the magnitude of F ab can signify the bonding character of the paired electrons as well as the diradical character of the unpaired electrons for both σ‐ and π‐types. Discarding the concept of the overlap between non‐orthogonal atomic orbitals, the different orbitals for different spins in the unrestricted Hartree‐Fock wavefunction reveal that there are three pairs of opposite spin density flows between two atoms, which proceed until the bonding molecular orbitals form.