Electron spin resonance studies of \u3csup\u3e199\u3c/sup\u3eHgH, \u3csup\u3e201\u3c/sup\u3eHgH, \u3csup\u3e199\u3c/sup\u3eHgD and \u3csup\u3e201\u3c/sup\u3eHgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (Adip) and isotropic (Aiso) components of the nuclear hyperfine interactions have been directly measured for 199Hg, 201Hg, H and D. Electronic structure information for HgH in its X2Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with Aiso(199Hg) = 6859(3), Adip(199Hg) = 446(3), Aiso(H) = 730(2) and Adip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be..