Theoretical study of the bonding in Mn+-RG complexes and the transport of Mn+ through rare gas, (M=Ca, Sr, and Ra; n=1 and 2; and RG=He-Rn)
ABSTRACT We present high level ab initio potential energy curves for the M(n+)-RG complexes, where n=1 and 2; RG=He-Rn; and M=Ca, Sr, and Ra. Spectroscopic constants have been derived from these potentials and are compared with a wide range of experimental and previous theoretical data, and good agreement is generally seen. Large changes in binding energy, D(e), and bond length, R(e), between M(+)-He, M(+)-Ne, and M(+)-Ar, also found previously in the analogous Ba(+)-RG complexes [M. F. McGuirk et al., J. Chem. Phys. 130, 194305 (2009)], are identified and the cause investigated; the results shed light on the previous Ba(+)-RG results. These unusual trends are not observed for the dicationic complexes, which behave in a fashion similar to the isoelectronic alkali metal ion complexes. The potentials have also been employed to calculate transport coefficients for M(n+) moving through a bath of rare gas (RG) atoms.
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ABSTRACT: Potential energy curves for the interaction of B(+) ((1)S) with RG ((1)S), RG = He-Rn, have been calculated at the CCSD(T) level of theory employing quadruple-ζ and quintuple-ζ quality basis sets. The interaction energies from these curves were subsequently point-by-point extrapolated to the basis set limit. Rovibrational energy levels have been calculated for each extrapolated curve, from which spectroscopic parameters are determined. These are compared to previously determined experimental and theoretical values. The potentials have also been employed to calculate the transport coefficients for B(+) traveling through a bath of RG atoms. We also investigate the interactions between B(+) and the rare gases via contour plots, natural population analysis (NPA), and molecular orbital diagrams. In addition, we consider the atoms-in-molecules (AIM) parameters. The interactions here are compared and contrasted with those for Li(+)-He and Be(+)-RG; it is concluded that there is significant and increasing dative covalent bonding for the Be(+)-RG and B(+)-RG complexes for RG = Ar-Rn, while the other species are predominantly physically bound.The Journal of Physical Chemistry A 04/2012; 116(20):4995-5007. DOI:10.1021/jp303057x · 2.78 Impact Factor
Article: Diatomic dications and dianions[Show abstract] [Hide abstract]
ABSTRACT: Diatomic dications and dianions are attractive species for quantum chemists and spectroscopists. In comparison with neutral diatomics, these species show a wealth of potential behaviors arising mainly from the presence of residual Coulomb repulsion at the separated ions limit. Due to the stability of dications, numerous reports have been published on their potential curves, vibrational states, stability, and spectroscopic properties. In contrast, there are only a few reports on the stability and potential curves of dianions, since the strong correlation effects in dianions introduce some difficulties in the calculations of their potentials and properties, and perhaps, because they have not been observed in the laboratory due to their short lifetimes. In this review article, interesting subjects related to dications and dianions, the methods used to study their characteristics, and the achievements of these studies are described. Furthermore, the present research topics open on dications and dianions are reviewed. This report would thus serve researchers interested in the examination of quantum dynamical treatment on reactive scattering of ions and the laser–matter interactions and their subsequent phenomena such as vibrational wavepacket evolution, tunneling dissociation, vibronic coupling, and tunneling ionization for which dianions and dications can be regarded as prototypical species.Journal of the Iranian Chemical Society 06/2014; 11(3):871. DOI:10.1007/s13738-013-0359-5 · 1.41 Impact Factor
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ABSTRACT: The xenon-difluoronitrenium ion F(2)N-Xe(+) , a novel xenon-nitrogen species, was obtained in the gas phase by the nucleophilic displacement of HF from protonated NF(3) by Xe. According to Møller-Plesset (MP2) and CCSD(T) theoretical calculations, the enthalpy and Gibbs energy changes (ΔH and ΔG) of this process are predicted to be -3 kcal mol(-1) . The conceivable alternative formation of the inserted isomers FN-XeF(+) is instead endothermic by approximately 40-60 kcal mol(-1) and is not attainable under the employed ion-trap mass spectrometric conditions. F(2)N-Xe(+) is theoretically characterized as a weak electrostatic complex between NF(2)(+) and Xe, with a Xe-N bond length of 2.4-2.5 Å, and a dissociation enthalpy and free energy into its constituting fragments of 15 and 8 kcal mol(-1), respectively. F(2)N-Xe(+) is more fragile than the xenon-nitrenium ions (FO(2)S)(2)NXe(+), F(5)SN(H)Xe(+), and F(5)TeN(H)Xe(+) observed in the condensed phase, but it is still stable enough to be observed in the gas phase. Other otherwise elusive xenon-nitrogen species could be obtained under these experimental conditions.Chemistry - A European Journal 09/2011; 17(38):10682-9. DOI:10.1002/chem.201101395 · 5.70 Impact Factor