We present a new chemical mechanism for Hg0/HgI/HgII atmospheric cycling, including recent laboratory and computational data, and implement it in the GEOS-Chem global atmospheric chemistry model for comparison to observations. Our mechanism includes the oxidation of Hg0 by Br and OH, subsequent oxidation of HgI by ozone and radicals, respeciation of HgII in aerosols and cloud droplets, and speciated HgII photolysis in the gas and aqueous phases. The tropospheric Hg lifetime against deposition in the model is 5.5 months, consistent with observational constraints. The model reproduces the observed global surface Hg0 concentrations and HgII wet deposition fluxes. Br and OH make comparable contributions to global net oxidation of Hg0 to HgII. Ozone is the principal HgI oxidant, enabling the efficient oxidation of Hg0 to HgII by OH. BrHgIIOH and HgII(OH)2, the initial HgII products of Hg0 oxidation, respeciate in aerosols and clouds to organic and inorganic complexes, and volatilize to photostable forms. Reduction of HgII to Hg0 takes place largely through photolysis of aqueous HgII–organic complexes. 71% of model HgII deposition is to the oceans. Major uncertainties for atmospheric Hg chemistry modeling include Br concentrations, stability and reactions of HgI, and speciation and photoreduction of HgII in aerosols and clouds.

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Relativistic effects in atomic and molecular propertiesWe present an overview of basic principles and methods of the relativistic quantum chemistry. Practical aspects of different methods will be discussed stressing their capability of providing accurate predictions of molecular properties, particularly in species containing a heavy metal element. We will present a series of examples showing the importance of relativistic effects in a variety of molecular properties including electron affinities, ionization potentials, reaction and dissociation energies, electric, spectroscopic and other properties. It is possible to recognize a link between these properties and behaviour of materials in some cases. Particular attention is paid to relativistic calculations of the nuclear quadrupole moments for which accurate theoretical electric field gradient is combined with data from the microwave spectra. Important aspect of the present paper is understanding of trends in electronically related atoms throughout the Mendeleev Periodic Table rather than focusing on highly accurate numbers. We will show that relativistic effects represent an unavoidable instrument for explaining some unexpected properties of heavy metal containing compounds. We will also discuss an interplay between the many-electron correlation and relativistic effects.

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ABSTRACT:The effect of the so-called picture change on expectation values of Ž . one-electron operators in approximate two one -component relativistic theories is discussed. This effect is expected to be particularly large for operators which assume large values in the vicinity of heavy nuclei. The numerical results illustrating the picture change effect on electric field gradients at nuclei have been obtained in the spin-free Pauli and Douglas᎐Kroll approximations. It has been found that the picture change effect lowers the electric field gradient at I in HI by about 1 a.u. Very large picture change Ž . effect y8 a.u. has been calculated for HAt. It is concluded that in accurate calculations of expectation values of operators involving high inverse powers of the electron᎐nucleus distance the picture change, which accompanies the transformation of the Dirac Ž . Ž . Dirac᎐Coulomb equation to approximate two one -component relativistic Hamiltonians, must be taken into account.