Relativistic effects in chemistry
- L.V. Pisarzhevskii Inst. of Physical Chemistry, Kiev (Ukraine)
Relativistic effects become apparent when the velocity of the electron is arbitrarily close to the speed of light (137 au) without actually attaining it (in heavy atoms of elements at the end of Mendeleev`s Periodic Table). At the orbital level, the relativistic effect is apparent in the radial contraction of penetrating s and p shells, expansion of nonpenetrating d and f shells, and the spin-orbit splitting of p-,d-, and f-shells. The appearance of a relativistic effect is indicated in the variation in the electronic configurations of the atoms in the Periodic Table, the appearance of new types of closed electron shells (6s{sub 1/2}{sup 2}, 6p{sub 1/2}{sup 2}, 7s{sub 1/2}{sup 2}, 5d{sub 3/2}{sup 4}), the stabilization of unstable oxidation states of heavy elements, the characteristic variation in the ionization enthalpies of heavy atoms, their electron affinity, hydration energies, redox potentials, and optical electronegativities. In the spectra of coordination compounds, a relativistic effect is observed when comparing the position of the charge transfer bands in analogous compounds, the parameters characterizing the ligand field strength (10Dq), the interatomic distances and angles in compounds of heavy elements. A relativistic effect is also apparent in the ability of heavy metals to form clusters and superclusters. Relativistic corrections also affect other properties of heavy metal compounds (force constants, dipole moments, biological activity, etc.).
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 161949
- Journal Information:
- Theoretical and Experimental Chemistry, Vol. 31, Issue 3; Other Information: PBD: Nov 1995; TN: Translated from Teoreticheskaya i Eksperimental`naya Khimiya; 31: No. 3, 181-199(May-Jun 1995)
- Country of Publication:
- United States
- Language:
- English
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