A Møller–Plesset study of the electron affinities of the diatomic hydrides XH (X=Li, B, Be, C, N, O)

Frenking, Gernot; Koch, Wolfram

doi:doi:10.1063/1.450832

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Theoretical determination of the indirect nuclear spin–spin coupling tensors, nuclear screening tensors, and magnetic susceptibilities of multiply bonded systems via the equations‐of‐motion method

In this paper we document the possible performances of the equations‐of‐motion method for predicting second‐order magnetic properties (indirect nuclear spin–spin coupling tensors, nuclear screening tensors, and magnetic susceptibilities). Nonempirical calculations for a series of molecules containing conjugated or cumulated multiple bonds and most of them suffering from UHF triplet instability are reported. In spite of the limitation of the 631G∗∗ basis set used, the results fit reasonably well ...

Ab initio SCF calculation on Li_nH_m molecules and cations with four or less atoms

All possible molecules and monopositive cations containing lithium and hydrogen, up to a total of four atoms, have been studied by ab initio calculations using SCF wave functions built from Gaussian‐type orbitals. The triatomic molecules and ions Li2H, Li3, H+3 , LiH+2 , Li2H+, and Li+3 were all found to be stable, i.e., of lower energy than any possible dissociation product. The neutral molecules H3 and LiH2 were found to be unstable relative to H2+H and Li+H2, respectively. The ions H+3 and Li...

Electron affinities for LiH, BeH, BH, CH, NH, and OH are computed at the MP2, MP3, and full MP4(SDTQ) order of perturbation theory employing the basis sets 6‐31G(d,p), 6‐311G(d,p), 6‐311++G(d,p), and 6‐311++G(3df,3pd), using geometries optimized at MP2/6‐31G(d,p). At the MP4(SDTQ)/6‐311++G(3df,3pd)//MP2/6‐31G(d,p) level including zero‐point corrections, electron affinities are predicted with a maximum deviation of 0.2 eV from experiment. At the same level of theory, dissociation energies of the anions are computed to an accuracy of 0.11 eV. The energy results reported here are in most cases in better agreement with experiments than previous theoretical results. Vibrational frequencies and atomic distances are determined at the MP2/6‐31G(d,p) level indicating longer bonds and lower frequencies as a consequence of electron attachment to the neutral hydrides.

KEYWORDS and PACS

Keywords

AFFINITY, ELECTRONEGATIVITY, LITHIUM HYDRIDES, BERYLLIUM HYDRIDES, HYDROXYL RADICALS, METHYLENE RADICALS, NITROGEN HYDRIDES, VIBRATIONAL STATES, BOND LENGTHS, DIATOMIC MOLECULES, PERTURBATION THEORY, DISSOCIATION ENERGY

PACS

33.15.Ry

Ionization potentials, electron affinities, molecular core binding energy
33.20.Tp

Vibrational analysis
33.15.Fm

Bond strengths, dissociation energies