C. K. Jorgensen's Absorption Spectra and Chemical Bonding in Complexes PDF
By C. K. Jorgensen
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Extra info for Absorption Spectra and Chemical Bonding in Complexes
However, this statement is ambiguous, if the ionic charge Z 0 — 1 is not given. For neutral atoms, 3d has lower energy than 4s in hydrogen and the first other light atoms. The energies seem to cross about carbon, and both levels correspond here to highly excited states of the neutral atom. In the interval carbon (Z = 6) to calcium (Z = 20), 4s has 24 ORBITALS IN ATOMIC SPECTROSCOPY distinctly lower energy than 3d. Around Ζ = 22, it may still be questionable which has the lower energy, but 3d is distinctly creeping below 4s.
However, the rest, the correlation energy (defined as the difference between the lowest obtainable HFSC-energy with one configuration and the observed value, corrected for relativistic effects) is not small compared to the usual chemical bonding energies in molecules. If it changes by the formation of molecules from atoms, it will influence the bond energies most severely. The correlation energy is remarkably constant, 2 + 3 4 + 9-2 to 9-9 kK, in the isoelectronic series He, Li+, B e , B +, C .
A^) - k t k t (a a :b a )] (29) The signs in eqn. (28) and (29) are related to the choice of phases of the wave functions. The diagonal element of a given configuration consists of a double summation Σ [(a^iaV) - k>t (a¥:a¥)] (30) THE ENERGY LEVELS OF A C O N F I G U R A T I O N 39 Here, only two electrons are involved at a time, and it is convenient to define two types of integrals Coulomb integral J(a, b) = (aa:bb) exchange integral K(a, b) = (ab:ab) (31) where the first is the classical interaction between the two extended 2 2 charge distributions ψ& and φ^ , while the exchange integral is the less familiar interaction of φ^ψκ with itself.
Absorption Spectra and Chemical Bonding in Complexes by C. K. Jorgensen