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In the present work, we investigate the bonding, structures, stability and spectra of the Zn(q+)Im (where q = 0, 1, and 2) complexes, which are zeolitic imidazolate frameworks (ZIFs) and Zn-enzyme sub-units. Through a benchmark work, we used density functional theory (DFT) with dispersion correction and standard and explicitly correlated ab initio methods. For neutral Zn(0)Im, we found two stable weakly bound forms: (i) a stacked ferrocene-like complex and (ii) a planar σ-type complex. This is the first report of the Zn(0) organic compound with a stacked ferrocene-like structure. The most stable isomers of the ionic species consist of σ-type bonded complexes. The role of various types of covalent and noncovalent interactions within these complexes is discussed after performing vibrational, NBO, charge and orbital analyses. For neutral species, van der Waals (vdWs) and charge transfer through covalent as well as noncovalent interactions are in action; whereas the bonding is dominated by charge transfer from Zn to Im within the ionic species. These findings are important to understand, at the microscopic level, the structure and the bonding within the ZIFs and the Zn-enzymes. Moreover, we establish the ability and reliability of M05-2X and PBE0 functionals for the simultaneous correct description of covalent and noncovalent interactions since this DFT leads to a close agreement with post-Hartree-Fock methods. The newly launched M11 functional is also suited for the description of noncovalent interactions. Therefore, M05-2X and PBE0 functionals are recommended for studying the larger complexes formed by Zn and Im, such as the ZIFs and Zn-enzymes.

Semilocal pseudopotential operators can be expressed as a linear combination of nonlocal (projection) operators. Pseudopotential operator integrals over a molecular basis set are therefore reduced to linear combinations of overlap integrals products. Molecular calculations indicate that sufficient precision can be achieved with a limited number of nonlocal operators. Analytic derivatives of pseudopotential integrals are easily deduced and implemented in a standard quantum chemistry program.

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