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XeCu covalent bonding in XeCuF and XeCuCl, characterized by Fourier transform microwave spectroscopy supported by quantum chemical calculations

TitleXeCu covalent bonding in XeCuF and XeCuCl, characterized by Fourier transform microwave spectroscopy supported by quantum chemical calculations
Publication TypeJournal Article
Year of Publication2006
AuthorsMichaud, JM, Gerry, MCL
JournalJournal of the American Chemical Society
Volume128
Pagination7613-7621
Date PublishedJun
Type of ArticleArticle
ISBN Number0002-7863
KeywordsAB-INITIO, DIPOLE MOMENTS, ELECTRIC-RESONANCE METHOD, GAUSSIAN-BASIS SETS, HYPERFINE CONSTANTS, KR, LASER-ABLATION, MOLECULAR CALCULATIONS, ROTATIONAL SPECTRA, VANDERWAALS COMPLEX
Abstract

XeCu covalent bonding has been found in the complexes XeCuF and XeCuCl. The molecules were characterized by Fourier transform microwave spectroscopy, supported by MP2 ab initio calculations. The complexes were prepared by laser ablation of Cu in the presence of Xe and SF6 or Cl-2 and stabilized in supersonic jets of Ar. The rotational constants and centrifugal distortion constants show the XeCu bonds to be short and rigid. The Xe-131, Cu, and Cl nuclear quadrupole coupling constants indicate major redistributions of the electron densities of Xe and CuF or CuCl on complex formation which cannot be accounted for by simple electrostatic effects. The MP2 calculations corroborate the XeCu bond lengths and predict XeCu dissociation energies similar to 50- 60 kJ mol(-1). The latter cannot be accounted for in terms of induction energies. The MP2 calculations also predict valence molecular orbitals with significant shared electron density between Xe and Cu and negative local energy densities at the XeCu bond critical points. All evidence is consistent with XeCu covalent bonding.

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