Isoelectronic analogues of PN: Remarkably stable multiply charged cations

Journal Article · Thu Jan 25 00:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100365a026· OSTI ID:6652807

Wong, Ming Wah; Radom, L ^[1]

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1. Australian National Univ., Canberra, Australian Capital Territory (Australia)

The structures and stabilities of PN and its 27 isoelectronic analogues, CS, SiO, BCl, AlF, BeAr, MgNe, Sn{sup +}, PO{sup +}, CCl{sup +}, SiF{sup +}, BAr{sup +}, AlNe{sup +}, SO{sup 2+}, NCl{sup 2+}, PF{sup 2+}, CAr{sup 2+}, SiNe{sup 2+}, OCl{sup 3+}, SF{sup 3+}, NAr{sup 3+}, PNe{sup 3+}, FCl{sup 4+}, OAr{sup 4+}, SNe{sup 4+}, FAr{sup 5+}, ClNe{sup 5+}, and ArNe{sup 6+}, have been examined by ab initio molecular orbital theory. The CASSCF/6-311G(MC)(d) level was used to determine the ground-state potential energy curves and spectroscopic constants for the 28 diatomic systems. Equilibrium structures were also obtained with the 6-311G(MC)(d) basis set at the MP3 and ST4CCD levels, and dissociation energies were determined at the MP4/6-311 + G(MC)(2df) and MP4/6-311 + G(MC)(3d2f) levels. For the neutral and monocation analogues of PN, the calculated equilibrium geometries (at MP3/6-311G(MC)(d)) and dissociation energies (at MP4/6-311 + G(MC)(3d2f)) are in very good agreement with available experimental values. All the dication analogues of PN, namely, SO{sup 2+}, NCl{sup 2+}, PF{sup 2+}, CAr{sup 2+}, and SiNe{sup 2+}, are predicted to be experimentally observable species. Of these, the SO{sup 2+}, NCl{sup 2+}, and CAr{sup 2+} dications are calculated to be kinetically stable species, with large barriers associated with the exothermic charge-separation reactions, while the PF{sup 2+} and SiNe{sup 2+} dications are predicted not only to be kinetically stable but also to be thermodynamically stable species.

• OSTI ID: 6652807
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 94:2; ISSN 0022-3654
• Country of Publication: United States
• Language: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
NITROGEN
ANALOG SYSTEMS
BERYLLIUM COMPOUNDS
BORON COMPOUNDS
CHARGE STATES
CHLORINE COMPOUNDS
COMPUTER CALCULATIONS
FLUORINE COMPOUNDS
IONS
ISOELECTRONIC ATOMS
PHOSPHORUS COMPOUNDS
SILICON COMPOUNDS
SULFUR COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
ATOMS
CHARGED PARTICLES
ELEMENTS
HALOGEN COMPOUNDS
NONMETALS
400201* - Chemical & Physicochemical Properties
360603 - Materials- Properties
990200 - Mathematics & Computers