The Fock Matrix Analysis for Atomic Orbitals in Molecular Orbitals. A New Look on the Covalent Bond in H2+ and H2

• Main Authors: Kuo-Kong Chen, 陳國光
• Other Authors: Shao-Pin Wang
• Format: Others
• Language: zh-TW
• Published: 2002
• Online Access: http://ndltd.ncl.edu.tw/handle/40217133892107537843

碩士 === 國立成功大學 === 化學系碩博士班 === 90 === The Fock operator can take all interaction within the molecular environment into account, therefore the character of the molecular orbitals can be better accounted for in terms of molecular adapted atomic orbitals and the Fock matrix expanded in these atomic orbital set. Within the independent particle approximation only the eigenvalues and the eigenstates of the Fock operator are meaningful.Attempt to associate the coefficients in the LCAO-MO ＝ ＋ )with the meaning of probability often leads to ambiguous results because the AOs and in the LCAO-MO are not the eigenstates of the Fock operator and thus they are not the assumed atomic orbitals. Instead of the picture that overlap charge migrates into the bonding region, the new analysis display another picture that the charge densities for the electron with α(orβ) spin gives rise to spin density flow. Thus a criterion for the covalent bond in the one-electron MO level can be defined according to the Fock matrix analysis.