Accurate potential energy curves for Zn+–Rg (Rg=He–Rn): Spectroscopy and transport coefficients

Hybridization and Covalency in the Group 2 and Group 12 Metal Cation/Rare Gas Complexes

“…The key experimental data 33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52 are displayed in Tables 1 and 2, as well as comparisons between the present and our previous work. Since these complexes have been previously studied using subsets of the approaches taken here, and in those studies generally very good agreement between previous theoretical and experimental work was seen, 6,7,8,9,12,13 a full survey of previous experimental and theoretical studies is not repeated herein. In most cases, those experimental results are spectroscopic studies and it was possible to compare to the calculated spectroscopic constants.…”

“…The previous IECs from our group for the titular species were also used to calculate ion transport coefficients and this provided another avenue of comparison by which to evaluate the quality of the calculated potentials via ion transport studies of metal cations moving through a bath of rare gas. [7][8][9]12,13 Some comment will, however, be made on several studies that have been published since that earlier work. For the Be + −RG and Mg + −RG complexes, the new IECs are almost identical to those published previously 9 (since there were only minimal changes to the basis sets between the two studies).…”

“…Unfortunately, at that time, consistent basis sets were not available for the whole set of group 2 metals and so custom-designed ones were employed in some cases, albeit to match the quality of standard Dunning-style aug-cc-pV5Z basis sets combined with an effective core potential for the heavier species. A similar situation occurred with the group 12 species, , but also at that time a detailed analysis of the interactions was not undertaken.…”

“…Being able to study families of systems where these regimes are traversed is expected to increase our understanding of chemical bond formation. As such, many theoretical studies have been undertaken previously by our group on M + –RG systems (RG = He–Rn), with the metals coming from group 1, − group 2, − group 11, , group 12, , and group 13. − These studies have used CCSD­(T) or RCCSD­(T) theory with large basis sets to calculate interaction energy, E int , curves (IECs), often extrapolated to the basis set limit. These IECs have been employed to obtain spectroscopic constants and to calculate transport coefficients for the metal cations moving in inert gases.…”

Theoretical Study of M+−RG and M2+−RG Complexes and Transport of M+ through RG (M = Be and Mg, RG = He−Rn)

“…For He−Ar, the standard aug-cc-pVQZ and aug-cc-pV5Z basis sets – were employed; for Kr−Rn the basis sets employed were the small-core relativistic effective core potentials (ECPs), ECP10MDF, ECP28MDF, and ECP60MDF for Kr, Xe, and Rn, respectively; these were used in conjunction with the aug-cc-pV5Z-PP valence basis sets . Additionally, we included tight functions to describe the correlation of the inner-valence d orbitals (see ref for functions and exponents). For beryllium and magnesium, aug-cc-pVQZ and aug-cc-pV5Z basis sets were employed, but each was augmented with tight functions of each angular momentum type, to allow description of core−valence correlation. , Each of the basis sets was augmented by an additional set of diffuse basis functions of each angular momentum type, obtained in an even-tempered way from the two lowest exponents in each case, so that each basis set was overall doubly augmented with diffuse functions.…”