15min:
HYDROGEN INTERACTION WITH METAL HALIDES: THE NUCLEAR QUADRUPOLE COUPLING CONSTANT OF GOLD IN THE p -H2-AuCl COMPLEX AND TRENDS IN THE OTHER HYDROGEN-COINAGE METAL HALIDE INTERACTIONS.

DANIEL A. OBENCHAIN, G. S. GRUBBS II, HERBERT M. PICKETT AND STEWART E. NOVICK, Department of Chemistry, Wesleyan Univeristy, 52 Lawn Avenue, Middletown, CT, 06459-0180, USA .

The rotational spectrum of p -H2-AuCl has been measured using a laser ablation equipped FTMW cavity spectrometer. The predicted structure, using a 60 electron core potential and an aug-cc-pVQZ at the MP2 level of theory, shows that H2 has an re = 0.91Å. A predicted value for the eQq ( chiaa) of gold required a semi-empirical method using the results of previous AuCl complexes in the gas phase. Transitions have been measured across multiple J levels, and have been used to determine the rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants of multiple isotopologues. The o -H2-AuCl has also been observed. While the monomer value of the eQq of 197Au was determined to be 9.63112(13) MHz in 197Au35Cl, we observed a significant change in the eQq of 197Au in p -H2-197Au35Cl to a value of -817.9983(36) MHz [0.02728556(12) cm-1], giving rise to a Au hyperfine component splittings of approximately 220 MHz [0.007 cm-1] and suggesting a change in electronic structure with the interaction of H2. We will present a summary of the hydrogen-coinage metal halide talks given at this conference, including trends in eQq and hydrogen metal halide dissociation energies.