Theoretical investigations of structural, thermal properties and stability of the group 12 metal M(XH) isomers in atmosphere: M = (Zn, Cd, Hg) and XH = (OH, SH)

• Published in: Theoretical chemistry accounts Vol. 138; no. 9; pp. 1 - 14
• Main Authors: Ezarfi, N., Touimi Benjelloun, A., Sabor, S., Benzakour, M., Mcharfi, M.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.09.2019; Springer Nature B.V
• Subjects: Atomic/Molecular Structure and Spectra; Cadmium; Chemistry; Chemistry and Materials Science; Electronic properties; Electronic structure; Energy of dissociation; Enthalpy; Free energy; Heat of formation; Hyperspaces; Inorganic Chemistry; Isomerization; Isomers; Mathematical analysis; Organic Chemistry; Physical Chemistry; Regular Article; Relativism; Relativistic effects; Solar radiation; Theoretical and Computational Chemistry; Thermodynamic properties; Zinc; Hypersurface; A; Electronic structure; DFT; Atmosphere; Isomerization; Dissociation
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-019-2499-x

Electronic structure calculations have been performed of the group 12 metal (Zn, Cd, Hg) reaction between hydroxyl OH and hydrosulfide SH to understand the processes of transformation in the atmosphere. DFT/B3LYP methods are employed to calculate the structure of reactants, intermediates, transition states and products as well as their equilibrium geometries, electronic properties, dissociation energy. The scalar relativistic effects have been accurately included by making use of the relativistic effective potentials. The computing results obtained at B3LYP/MWB level of M(OH) and M(SH) for doublet and quartet ( 2,4 ∑ + , 2 A′, 4 A″ and 2,4 ∏) state suggest that the doublet states are most stable than the quartet. The computed potential hypersurface 2 A′ indicates four stationary points; two of them correspond to the stable structures with symmetries: MOH/MSH( 2 A′) and OMH/SMH( 2 ∏), and two points correspond to transition states with the symmetries: MOH/MSH( 2 ∑ + ) and MOH/MSH( 2 A′). The isomerization process MXH( 2 A′) → XMH( 2 ∏) via the transition state and the atmospheric stability of M(XH) are also discussed. Examination of dissociation energy, enthalpy of reaction and wavelength from linear form OMH/SMH( 2 ∏) estimate that the molecule has appreciable stability. As for the angled form MOH/MSH( 2 A′), the values obtained suggest that it is easily dissociable in the presence of solar radiation. Our results are compared with previous work, when available.