Static and dynamic structure of monomers, dimers and trimers of HgCl2 from density-functional calculations

Ruberto, R.; Pastore, G.; Özen, Alimet Sema; Akdeniz, Z.; Tosi, M. P.

doi:10.1140/epjd/e2012-30235-9

Cited by 11 publications

(27 citation statements)

References 22 publications

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“…We rely on the methods of relativistic density functional theory (DFT), using expansions of the Kohn-Sham orbitals in sets of localised Gaussians. It was shown in an earlier work on HgCl 2 [4] that this yields results in close agreement with those obtained by an expansion into plane waves.…”

Section: Introductionsupporting

confidence: 85%

“…[2] It is clear from Table 1 that the role of relativistic effects is minor in the compounds of Zn and Cd. As discussed more fully in, [4] the main consequence of their inclusion in the Hg dihalides is a shortening of the bond length in the monomer by about 0.02 nm, accompanied by a strong stiffening of the monomer against bending. The relativistic contraction of the outer electron shells of the Hg atom increases the mixing of ionic and covalent character.…”

Section: Calculational Procedures and Tests On Monomers And Dimersmentioning

confidence: 92%

“…[1,2] This connection is well established for HgCl 2 , where the Cl-Hg-Cl monomers are the basic constituents of the dimer, [2,3] the trimer, [4,5] and the condensed liquid and crystal phases. [6] On the other hand, tetrahedral coordination of the metal ion is dominant in the condensed phases of Zn dihalides [7] and in the liquid phase of CdCl 2 and CdBr 2 , [8,9] freezing being accompanied in the two latter compounds by a transition from fourfold to sixfold coordination.…”

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

Structure of trimers of group-2B metal dihalides from relativistic density-functional calculations

Özen

Akdeniz

Pastore

et al. 2014

Physics and Chemistry of Liquids

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We report density-functional calculations, carried out in a quantum-chemical approach using localised-Gaussians expansions of the Kohn–Sham orbitals, for metal dihalides trimers (MX2)3, where X = Cl, Br, or I and M = Zn, Cd, or Hg. The reliability of the method and the relevance of relativistic terms are assessed by comparisons with previous results on bond lengths in the monomer and dimer of these compounds. In\ud a viewpoint regarding the trimer as a possible structural component of expanded liquid states and of compressed gaseous states, we stress the character of the local coordination of the metal ion in the ground state as being of a distorted tetrahedral type in the case of the trimer of the Zn and Cd dihalides and of a twofold type in the Hg dihalides.\ud We also discuss the presence of metastable and unstable structures at higher energies and the quantum-chemical topology of the trimer

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Section: Introductionsupporting

confidence: 85%

Section: Calculational Procedures and Tests On Monomers And Dimersmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 97%

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Structure of trimers of group-2B metal dihalides from relativistic density-functional calculations

Özen

Akdeniz

Pastore

et al. 2014

Physics and Chemistry of Liquids

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“…This functional gave the best performance with these systems as stated in a previous benchmark study. 1 6-311+G* basis set was employed for Zn, F, Cl, and Br atoms. Relativistic effects were introduced by using the ECP60MWB basis set, which incorporates the Wood−Boring quasirelativistic effective core potential, for mercury and ECP28MWB for cadmium.…”

Section: ■ Introductionmentioning

confidence: 99%

Chemical Reactivity Perspective into the Group 2B Metals Halides

Özen

Akdeniz

2016

J. Phys. Chem. A

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Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

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“…1b, c), especially for the mercury systems, which are also quite weakly bound. The geometrical distortions necessary to optimize orbital interactions, charge transfer, and short bond distances between the HgX 2 monomers are costly, and those costs are not compensated for by the energy lowering that the HgX 2 ÁÁÁHgX 2 (inter-monomer) interactions in the theoretical D 2h geometry afford [4,[27][28][29]. And the story becomes even more interesting: The inflexibility of the monomers appears to propagate all the way through to the solids in some cases, but apparently not in others [4].…”

Section: Introductionmentioning

confidence: 99%

Structure, bonding, relativistic effects, and dispersion in the group 12 dihalide (MX2)3 clusters, with lessons from the extended solids

2015

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The prediction of crystal structures for inorganic solids remains a challenge at the frontier of materials science. We examine the relationship between the group 12 dihalide monomers, small oligomers (in particular the trimers), and the extended solids. The clusters are investigated at density functional B3PW91 and MP2 computational levels and at the M06-2X, B97D3, and CCSD(T) levels for the first time for special cases where dispersion is important. Significant patterns in the bonding preferences in the dimers and extended solids of these systems are known to reflect the rigidity of the linear monomers. The trimers evolve typically as one-dimensional extensions of the dimers, but the HgX 2 systems are different: They form loosely bound clusters with a few competitive geometries emerging that imply several potential directions for continued and more strongly bond higher-order clusters. The very weak intermolecular interactions in the Hg systems appear only when relativistic effects are turned on. Otherwise, they behave precisely like their Zn and Cd analogues. The HgF 2 trimers, which have not been considered before, are examined in detail as well. These trimers-especially the fluorides-are somewhat more polar than the isolated monomers and dimers, and we find evidence for a gradual switch to the ionic bonding regime in the HgF 2 clusters on the way to the fluorite extended solid structure. Differences between geometrical preferences obtained at the MP2 versus the B3PW91 levels for the (HgX 2 ) 3 clusters demonstrate the importance of dispersion interactions in the bonding. Successes are reported for other density functional methods that directly address dispersion.

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Static and dynamic structure of monomers, dimers and trimers of HgCl2 from density-functional calculations

Cited by 11 publications

References 22 publications

Structure of trimers of group-2B metal dihalides from relativistic density-functional calculations

Structure of trimers of group-2B metal dihalides from relativistic density-functional calculations

Chemical Reactivity Perspective into the Group 2B Metals Halides

Structure, bonding, relativistic effects, and dispersion in the group 12 dihalide (MX2)3 clusters, with lessons from the extended solids

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