DFT analysis of the interaction between Hg2+ and monodentate neutral ligands using NBO, EDA, and QTAIM

Silva, Victor Hugo Malamace da; Carneiro, José Walkimar de M.; Costa, Leonardo Moreira da; Ferreira, Gláucio B.

doi:10.1007/s00894-020-04413-5

Cited by 6 publications

(7 citation statements)

References 52 publications

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“…Although both binding free energies (in the gas phase) and solvation free energies are negative (see Table ), they reveal opposite results, with closed-shape clusters (highly coordinated) being the most likely configurations in an aqueous environment. In line with previous experimental − , and theoretical ,,,− studies, [Hg(H 2 O) 1–6 ] (aq) 2+ clusters structure is highly coordinated.…”

Section: Resultssupporting

confidence: 88%

“…Researchers have studied the solvation process of Hg 2+ in water using experimental methods such as nuclear magnetic resonance (NMR) , and X-ray diffraction , as well as theoretical methods, including density functional theory (DFT) with pseudopotentials, ,,− molecular dynamics, and hybrid quantum mechanics/molecular mechanics methods. ,− …”

Section: Introductionmentioning

confidence: 99%

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Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis

Florez,

Zapata-Escobar,

Ferraro

et al. 2023

J. Phys. Chem. A

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Understanding the nature of the interaction between mercury(II) ions, Hg 2+ , and water molecules is crucial to describe the stability and chemical behavior of structures formed during solvation, as well as the conditions that favor the Hg 2+ coordination or inducing water hydrolysis. In our study, we explored exhaustively the potential energy surface of Hg 2+ with up to six water molecules. We analyzed electronic and Gibbs free energies, binding, and nuclear magnetic resonance parameters. We used the zeroth-order regular approximation Hamiltonian, including scalar and spin−orbit relativistic corrections for free energy calculations and geometry optimizations to explore the interplay between electron correlation and relativistic effects. We analyzed intermolecular interactions with energy decomposition analysis, quantum theory of atoms in molecules, and natural bond orbital. Additionally, we used the fourcomponent Dirac Hamiltonian to compute solvent effect on the magnetic shielding and J-coupling constants. Our results revealed that the water hydrolysis by Hg 2+ requires a minimum of three water molecules. We found that the interaction between Hg 2+ and water molecules is an orbital interaction due to relativistic effects and the most stable structures are opened-shape clusters, reducing the number of oxygen−mercury contacts and maximizing the formation of hydrogen bonds among water molecules. In these types of clusters, Hg 2+ promotes the water hydrolysis over coordination with oxygen atoms. However, when we considered the change associated with the transfer of a cluster from the ideal gas to a solvated system, our solvation free energy analysis revealed that closedshape clusters are more favorable, maximizing the number of oxygen−mercury contacts and reducing the formation of hydrogen bonds among water molecules. This finding suggests that, under room conditions, the coordination of Hg 2+ is more favorable than hydrolysis. Our results have significant implications for understanding Hg 2+ behavior in water, helping to develop targeted strategies for mercury remediation and management, and contributing to advancements in the broader field of environmental chemistry.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis

Florez,

Zapata-Escobar,

Ferraro

et al. 2023

J. Phys. Chem. A

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“…All Ni( ii ) complexes are characterized with high exergonicities (Table 3), tying in with similar reports in the literature. 47 This is, at least partly, explained by a large electrostatic character of the formed complexes, being evident in a high charge transfer among interacting partners, between 0.10 and as much as 0.16 |e| (Table 3). In line with that, Ni( ii ) forms the least stable 1 : 1 complex with neutral water, Δ G INT = −67.7 kcal mol −1 , and accepts the least charge from that ligand.…”

Section: Resultsmentioning

confidence: 99%

A series of nickel(ii) thiocyanate complexes comprising various molar contents of isonicotinamide and water as ligands or co-crystallized moieties – an experimental and computational study

et al. 2022

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“…59 On the other hand, the phosphine oxide ligand shows higher affinity than most of the neutral N-and O-based donors due to the strong polarization of the P + -O À bond (Voronoi charge on O atom À0.433e, compared with À0.262e in water). 60 The Voronoi deformation density charges and Hirshfeld charges on donor atoms are listed in Tables 1 and 2. The more negative charges on donor atoms are linked to the magnitude of the ΔG.…”

Section: Relative Gibbs Free Energiesmentioning

confidence: 99%

“…Most of the neutral O-and N-donors exhibit similar values. A notable exception is the phosphine oxide OPPh 3 with ρ BCP = 0.057 a. u., which can again be attributed to the polarization of the PO bond 60. Systems with negatively charged donors have higher values of ρ BCP than the aqua complex (an exception is again perchlorate).…”

mentioning

confidence: 97%

Actinium coordination chemistry: A density functional theory study with monodentate and bidentate ligands

Tomeček

Schreckenbach

2022

J Comput Chem

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In the current study, the coordination chemistry of nine‐coordinate Ac(III) complexes with 35 monodentate and bidentate ligands was investigated using density functional theory (DFT) in terms of their geometries, charges, reaction energies, and bonding interactions. The energy decomposition analysis with naturals orbitals for chemical valence (EDA‐NOCV) and the quantum theory of atoms in molecules (QTAIM) were employed as analysis methods. Trivalent Ac exhibits the highest affinities toward hard acids (such as charged oxophilic donors, fluoride), so its classification as a hard acid is justified. Natural population analysis quantified the involvement of 5f orbitals on Ac to be about 30% of total valence electron natural configuration indicating that Ac is a member of the actinide series. Pearson correlation coefficients were used to study the pairwise correlations among the bond lengths, ΔG reaction energies, charges on Ac and donor atoms, and data from EDA‐NOCV and QTAIM. Strong correlations and anticorrelations were found between Voronoi charges on donor atoms with ΔG, EDA‐NOCV interaction energies and QTAIM bond critical point densities.

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DFT analysis of the interaction between Hg2+ and monodentate neutral ligands using NBO, EDA, and QTAIM

Cited by 6 publications

References 52 publications

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis

A series of nickel(ii) thiocyanate complexes comprising various molar contents of isonicotinamide and water as ligands or co-crystallized moieties – an experimental and computational study

Actinium coordination chemistry: A density functional theory study with monodentate and bidentate ligands

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DFT analysis of the interaction between Hg2+ and monodentate neutral ligands using NBO, EDA, and QTAIM

Cited by 6 publications

References 52 publications

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H2O)1–6](aq)2+: Insights from Relativistic Effects and Free Energy Analysis

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H2O)1–6](aq)2+: Insights from Relativistic Effects and Free Energy Analysis

A series of nickel(ii) thiocyanate complexes comprising various molar contents of isonicotinamide and water as ligands or co-crystallized moieties – an experimental and computational study

Actinium coordination chemistry: A density functional theory study with monodentate and bidentate ligands

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Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis

Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H₂O)_1–6]_(aq)²⁺: Insights from Relativistic Effects and Free Energy Analysis