Topic
Valence (chemistry)
About: Valence (chemistry) is a research topic. Over the lifetime, 24937 publications have been published within this topic receiving 645252 citations. The topic is also known as: valency.
Papers published on a yearly basis
Papers
More filters
240 citations
TL;DR: In this paper, a perturbational approach to relativistic calculations on molecules has been applied to a number of compounds containing heavy elements and the results show that the method is a viable alternative to more involved treatments.
Abstract: A recently proposed perturbational approach to relativistic calculations on molecules has been applied to a number of compounds containing heavy elements. Comparison of calculated spectroscopic constants with experiment and results from other theoretical models shows that the method is a viable alternative to more involved treatments. Relativistic corrections are essential for compounds containing heavy elements and result in a contraction of bond distances and a substantial change in bond energies. The perturbational approach lends itself readily to a straightforward interpretation of both effects. It appears that the bond contraction is not due to the relativistic contraction of valence atomic orbitals. It is a direct relativistic effect, the repulsion due to the rise in kinetic energy when bonds are shortened being diminished by the mass–velocity correction.
240 citations
TL;DR: The reactivity of the third-row transition-metal ions, both bare and with simple ligands, may be explained in terms of electronic structure considerations, such as promotion energy, exchange energy, and the relative and absolute sizes of the valence s and d orbitals as discussed by the authors.
Abstract: Methane is spontaneously dehydrogenated in the gas phase by many metal ions of the 5d transition series. In most cases, the MCH{sub 2}{sup +} produced undergoes further reactions, leading eventually to products such as WC{sub 8}H{sub 16}{sup +}. The reactivity of the third-row transition-metal ions, both bare and with simple ligands, may be explained in terms of electronic structure considerations. Promotion energy, exchange energy, and the relative and absolute sizes of the valence s and d orbitals all appear to be important.
239 citations
TL;DR: Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented and results are compared with available experimental data as well as with other theoretical data from the literature.
Abstract: Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.
239 citations
239 citations