title: Ab Initio and DFT Studies on CO2 Interacting with Zn(q+)-Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ- or π-Type Models.
abstract: Using first-principles methodologies, the equilibrium structures and the relative stability of CO2 @[Zn(q+) Im] (where q=0, 1, 2; Im=imidazole) complexes are studied to understand the nature of the interactions between the CO2 and Zn(q+) -imidazole entities. These complexes are considered as prototype models mimicking the interactions of CO2 with these subunits of zeolitic imidazolate frameworks or Zn enzymes. These computations are performed using both ab initio calculations and density functional theory. Dispersion effects accounting for long-range interactions are considered. Solvent (water) effects were also considered using a polarizable continuum model approach. Natural bond orbital, charge, frontier orbital and vibrational analyses clearly reveal the occurrence of charge transfer through covalent and noncovalent interactions. Moreover, it is found that CO2 can adsorb through more favorable π-type stacking as well as σ-type hydrogen-bonding interactions. The inter-monomer interaction potentials show a significant anisotropy that might induce CO2 orientation and site-selectivity effects in porous materials and in active sites of Zn enzymes. Hence, this study provides valuable information about how CO2 adsorption takes place at the microscopic level within zeolitic imidazolate frameworks and biomolecules. These findings might help in understanding the role of such complexes in chemistry, biology and material science for further development of new materials and industrial applications.
authors.affiliation: Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Échelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454, Marne-la-Vallée, France.
authors.forename: Reda
authors.initials: R
authors.lastname: Boulmene
authors.affiliation: Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Échelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454, Marne-la-Vallée, France.
authors.forename: Karim
authors.initials: K
authors.lastname: Boussouf
authors.affiliation: Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Échelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454, Marne-la-Vallée, France.
authors.forename: Muthuramalingam
authors.identifier: http://orcid.org/0000-0002-1886-7708
authors.initials: M
authors.lastname: Prakash
authors.affiliation: LS3 ME-Team of theoretical chemistry and modeling, Faculty of Sciences, University Mohammed V, Rabat, Morocco.
authors.forename: Najia
authors.initials: N
authors.lastname: Komiha
authors.affiliation: Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Kingdom of Saudi Arabia.
authors.forename: Muneerah M
authors.initials: MM
authors.lastname: Al-Mogren
authors.affiliation: Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Échelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454, Marne-la-Vallée, France. hochlaf@univ-mlv.fr.
authors.forename: Majdi
authors.initials: M
authors.lastname: Hochlaf
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D004798:Enzymes / Q000737:chemistry; D006860:Hydrogen Bonding; D007093:Imidazoles / Q000737:chemistry*; D007536:Isomerism; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory; D015032:Zinc / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D004798:Enzymes; D007093:Imidazoles; D002245:Carbon Dioxide; D015032:Zinc
keywords: CO2 adsorption and selectivity; Zn complexes; ab initio calculations; charge transfer; solvent effects