Mercury Is a Transition Metal: The First Experimental Evidence for HgF<sub>4</sub>

Wang, Xuefang; Andrews, Lester; Riedel, Sebastian; Kaupp, Martin

doi:10.1002/anie.200703710

Cited by 129 publications

(117 citation statements)

References 46 publications

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“…A recent paper by Jensen 4 suggests that Hg as well as Zn and Cd should not be classified as transition elements although some controversy still exists regarding this issue. 5,6 The ground state electronic configuration of mercury atom is [Xe] 4f 14 5d 10 6s 2 indicating that the Hg-dimer should be a weakly bound van der Waals-type system in its ground state. 7 Much attention has been dedicated to mercurycontaining compounds containing halogens and methyl groups that are of practical significance to the human population.…”

Section: Introductionmentioning

confidence: 99%

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Bytautas¹

2013

Croat. Chem. Acta

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Abstract. Dimethylmercury (CH 3 −Hg−CH 3 ) and other Hg-containing compounds can be found in atmospheric and aqueous environments. These substances are highly toxic and pose a serious environmental and health hazard. Therefore, the understanding of chemical processes that affect the stability of these substances is of great interest. The mercury-containing compounds can be detected in atmosphere, as well as soil and aqueous environments where, in addition to water molecules, numerous ionic species are abundant. In this study we explore the stability of several small, Hg-containing compounds with respect to water molecules, hydronium (H 3 O + ) ions as well as other small molecules/ions using density functional theory and wave function quantum chemistry methods. It is found that the stability of such molecules, most notably of dimethylmercury, can be strongly affected by the presence of the hydronium H 3 O + ions. Although the present theoretical study represents gas phase results, it implies that pH level of a solution should be a major factor in determining the degree of abundance for dimethylmercury in aqueous environment. In particular, it is found that CH 3 −Hg−CH 3 reacts readily with the H 3 O + ion producing CH 3 −Hg−OH 2 + and methane indicating that low-pH levels favor the decomposition of dimethylmercury. On the other hand, our study suggests that high-pH levels in aqueous environment would favor stronglybound complexes of [CH 3 −Hg−CH 3 OH]  species. Overall, the theoretical evidence presented in this study offers an explanation for the available experimental data concerning the stability of dimethylmercury and other mercury-containing compounds having the general structure

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Section: Introductionmentioning

confidence: 99%

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Bytautas¹

2013

Croat. Chem. Acta

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“…In CC calculations, all electrons except the 1s electrons of F are treated, which give rise to a total number of 315 orbitals and 48 electrons. The bond length, harmonic frequencies for HgF 4 and HgF 2 as well as the reaction energies for HgF 4 → HgF 2 + F 2 and HgF 4 → Hg + 2F 2 are listed in Table II, together with previous SR-CCSD(T) results 48,49,51 using the relativistic ECP developed by the Stuttgart group in 1993 52 and the same ECP as the present work, respectively. Contributions of basis-set superposition errors to reactions energies are also included using the counterpoise correction (CP) 53 at optimized structures.…”

Section: Resultsmentioning

confidence: 95%

“…The existence of the low-spin d 8 complex HgF 4 , which shows the transition-metal character of Hg, was only confirmed theoretically previously [46][47][48] and experimental evidence for its existence is not found until 2007. 49 In the present work, we investigate the structure, harmonic frequencies, as well as corresponding reaction energies related to HgF 4 using the present SO-CC approach. The ECP60MDF potential is adopted for Hg (Ref.…”

Section: Resultsmentioning

confidence: 99%

Symmetry exploitation in closed-shell coupled-cluster theory with spin-orbit coupling

Yang

Wang

et al. 2011

The Journal of Chemical Physics

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Orbital-optimized third-order Møller-Plesset perturbation theory and its spin-component and spin-opposite scaled variants: Application to symmetry breaking problems J. Chem. Phys. 135, 224103 (2011) Interaction energies of large clusters from many-body expansion J. Chem. Phys. 135, 224102 (2011) Local pair natural orbitals for excited states J. Chem. Phys. 135, 214106 (2011) Effect of microhydration on the guanidiniumbenzene interaction J. Chem. Phys. 135, 214301 (2011) Dispersion interactions in density-functional theory: An adiabatic-connection analysis J. Chem. Phys. 135, 194109 (2011) Additional information on J. Chem. Phys. In the present work, we report exploitation of spatial symmetry in calculations of ground state energy and analytic first derivatives of closed-shell molecules based on our previously developed coupledcluster (CC) approach with spin-orbit coupling. Both time-reversal symmetry and spatial symmetry for D 2h and its subgroups are exploited in the implementation. The symmetry of a certain spin case for the amplitude, intermediate, or density matrix is determined by the symmetry of the corresponding spin functions and the direct product decomposition method is employed in computations involving these quantities. The reduction in computational effort achieved through the use of spatial symmetry is larger than the order of the molecular single point group. Symmetry exploitation renders application of the CC approaches with spin-orbit coupling to larger closed-shell molecules containing heavy elements with high accuracy.

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“…The elements of Group 12 (Zn, Cd, Hg, Cn) were generally considered post-transition metals with filled (n -1)d shell. Irradiation of Hg and F 2 dispersed in solid neon or argon matrixes (T ≤ 10 K) with 240 -380 nm radiation emitted from a mercury arch led to the formation of square-planar HgF 4 molecules identified by IR spectroscopy (Wang et al, 2007). Involving its 5d orbitals in bonding, at least mercury may thus be declared a true transition metal.…”

Section: Driving Forces For Development Of Photochemistry -A Historicmentioning

confidence: 99%

Photochemistry — development and achievements

Šíma

2017

Acta Chimica Slovaca

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Photochemistry has been subjected to the enormous development within the last two centuries. This development has been driven mainly by two key factors: inherent scientific thirst for knowledge and worldwide foodstuff and energy needs. Within the development of photochemistry, mutual conditionality of global needs, progress in theory, improving of existing and birth of qualitatively new experimental techniques can be identified. Photochemistry has found its application in various fields of our life, development and protection of the nature.

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Mercury Is a Transition Metal: The First Experimental Evidence for HgF₄

Cited by 129 publications

References 46 publications

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Symmetry exploitation in closed-shell coupled-cluster theory with spin-orbit coupling

Photochemistry — development and achievements

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Mercury Is a Transition Metal: The First Experimental Evidence for HgF4

Cited by 129 publications

References 46 publications

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Symmetry exploitation in closed-shell coupled-cluster theory with spin-orbit coupling

Photochemistry — development and achievements

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Mercury Is a Transition Metal: The First Experimental Evidence for HgF₄