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

By C. K. Jorgensen

ISBN-10: 0080096271

ISBN-13: 9780080096278

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Extra resources for Absorption Spectra and Chemical Bonding in Complexes

Sample text

Since the correlation energy in the hydrogen molecule is now known to have the same magnitude as in He, we may still hope that the invariance with electron number also holds in the case of chemical bonding. Dr. Anders Fröman, Uppsala, has calculated the corre3+ lation energy in gaseous F" and A l to be 87 kK, by coincidence nearly the same value as found in the isoelectronic molecule HF. It is surprising for a chemist to know that a neon atom is stabilized with 250 kcal/mole more than would have been possible, if it had the lowest energy compatible with a pure inert-gas configuration 2 2 6 ls 2s 2p .

These "virtual" orbitals belong partly to the continuum of states, having higher energy of a given atom than necessary for the ionization of at least one electron to infinity. Virtual states may sometimes be rather well-defined in atomic spectroscopy; the first example discovered was the configuration 3d4d of neutral Ca, containing more energy than the ionized 4s of Ca+. g. the α-radioactive uranium nucleus is unstable against part-dissociation, but it has a half-life of milliards of years). It might seem a rather good performance of the HFSC-functions that ^ 9 9 per cent of the energy of the ground state of He can be 2 explained by a single configuration Is .

However, the decreased value of these interval ratios in the iso+ electronic series C, N , . . i s connected with the interaction with 2 n +2 rather than with "virtual" configurations, since the ratio ls 2p 4+ is remarkably constant for increasing ionic charge. In ions like 0 5 + X 2 2 and F , the highest term S of l s 2 p is strongly increased in energy, X 2 2 because of interaction with the ground state S of ls 2s . In these 3 ions, K(2s, 2p) can be estimated as half the distance between P and l 2 P of ls 2s2p and turns out to vary as a linear function of the ionic 2 7+ charge (in kK for Be 10-3, B+ 18-0, C + 25-0, .

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


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