C. K. Jorgensen's Absorption Spectra and Chemical Bonding in Complexes PDF

By C. K. Jorgensen

ISBN-10: 0080096271

ISBN-13: 9780080096278

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G. in neutral (but not highly ionized) atoms of the first transition group, the orbitals 3d and 4s have nearly the same energy, and therefore n 2 n+1 terms with the same L and S from the configurations 3d 4s , 3 d 4 s 46 THE ENERGY LEVELS OF A CONFIGURATION n +2 and 3 d are highly intermixed. But excepting these somewhat extraordinary cases, the validity of configurations will be highly dependent on whether we have chosen the orbitals in the most appropriate way. There is a fundamental difference between the non-diagonal elements of eqn.

4) that only s-electrons have a finite probability density close to the nucleus, while the positive /-values prevent a non-vanishing density, due to the "centrifugal" term of the kinetic energy. Generally, the behaviour of R for small values of r will be as a normalization factor l + 1 multiplied by r . For r -> oo, R of a stationary state vanishes exponentially as exp [—T\/(—Enl)] according to eqn. (4). Not only for a hydrogen atom, but for any of the central fields v 28 ORBITALS IN ATOMIC S P E C T R O S C O P Y found in atoms, the number of zero points of R (excluding those at r = 0 and r -> oo) is « — / — 1.

In the same way as the parameters of interelectronic repulsion can be used for defining an effective charge Z # (cf. eqn. 37), it is possible 2 to write ζη1 as a quadratic function k^Z^ , where the proportionality constant k nI varies surprisingly little within a given p- or d-shell. In this case, Z # is a linear function of the number of electrons q in the partly filled shell, being Z* = Z 0 + 0-5 + 0-7q for 4p<* and Z* = Z 0 — 0-8 + 0-8q for 4d<*. The factors are k 4P ~ 0 1 kK and k 4d ~ 0Ό29 kK, respectively.

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Absorption Spectra and Chemical Bonding in Complexes by C. K. Jorgensen

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