Relativistic effects in physics and chemistry of element 105. I. Periodicities in properties of group 5 elements. Electronic structure of the pentachlorides

Abstract

A detailed study of the electronic structure and bonding of the pentahalides of group 5 elements V, Nb, Ta, and element 105, hahnium (and Pa) has been carried out using relativistic molecular cluster Dirac–Slater discrete-variational method. A number of calculations have been performed for different geometries and molecular bond distances. The character of the bonding has been analyzed using the Mulliken population analysis of the molecular orbitals. It is shown that hahnium is a typical group 5 element. In a great number of properties it continues trends in the group. Some peculiarities in the electronic structure of HaCl5 result from relativistic effects.

Critical evaluation of the chemical properties of the transactinide elements (IUPAC Technical Report)

“…DS-DVM calculations [112][113][114][115] suggest that the pentahalides of Db should be more volatile than those of its lighter homologs. Experimental volatility studies have failed to demonstrate this.…”

“…DS DVM calculations allow prediction of the degree of covalency in the bonding and the effective charge on the central atom in halide and oxohalide compounds of the group 5 elements [112][113][114][115].…”

“…Atomic and ionic radii and the first through fifth ionization potentials were calculated in [111]. Differences between the chemical behavior of Db and the extrapolated properties of an eka-tantalum could result from a larger ionic radius, a different effective charge, and a different radial extension of the 6d orbitals, which are most important in its molecular bondings [100,[110][111][112][113][114][115]. Redox potentials were estimated for the group 5 elements, including the pseudohomolog Pa, on the basis of ionization potentials from MCDF calculations [111,116].…”

Aqueous-phase chemistry of the transactinides

“…Atomic and ionic radii and the first through fifth ionization potentials were calculated by Fricke et al [112]. Differences in the chemical behavior of element 105 to extrapolated properties of an eka-tantalum could result from a larger ionic radius, a different effective charge, and a different radial extension of the 6d orbitals which are most important in its molecular bondings (Pershina et al [113][114][115], Fricke et al [112], Pershina et al [116][117][118][119][120]). Redox potentials were estimated for the group-5 elements including the pseudo-homolog Pa on the basis of ionization potentials from MCDF calculations [112,121].…”

“…DS DVM calculations allow to determine the degree of covalency in the bonding and the effective charge on the central atom in halide and oxyhalide compounds of the group-5 elements [113][114][115][116].…”