Journal ArticleDOI
On the Stability of Interactions between Pairs of Anions – Complexes of MCl3− (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN−
TLDR
The ability of the central M atom of the MCl3 - anion, with M=Be, Mg, Ca, Sr, Ba, to engage in a noncovalent bond with an approaching nucleophile is gauged by ab initio methods.Abstract:
The ability of the central M atom of the MCl3 - anion, with M=Be, Mg, Ca, Sr, Ba, to engage in a noncovalent bond with an approaching nucleophile is gauged by ab initio methods. The N atom of pyridine forms a M⋅⋅⋅N bond with an interaction energy between 12 and 21 kcal mol-1 , even though the π-hole above the M atom is not necessarily positive in sign. Despite a strong Coulombic repulsion between two anions, CN- is also able to approach the M atom so as to engage in a metastable complex that is higher in energy than the individual anions. The energy barrier separating this complex from its constituent anion pair is roughly 20 kcal mol-1 . Despite the endothermic formation reaction energy of the CN- ⋅⋅⋅MCl3 - complex, the electron topology signals a strong interaction, more so than in pyridine⋅⋅⋅MCl3 - with its exothermic binding energy. The dianionic complex is held together largely on the strength of interorbital interactions, thereby overcoming a repulsive electrostatic component. The latter is partially alleviated by the pyramidalization of the MCl3 unit which makes its π-hole more positive. The complex sinks below the separate monomers in energy when the system is immersed in an aqueous medium, with a binding energy that varies from as much as 20 kcal mol-1 for Be down to 1.2 kcal mol-1 for Ba.read more
Citations
More filters
Journal ArticleDOI
Origins and properties of the tetrel bond
TL;DR: The tetrel bond (TB) recruits an element drawn from the C, Si, Ge, Sn, Pb family as electron acceptor in an interaction with a partner Lewis base as discussed by the authors.
Journal ArticleDOI
Understanding noncovalent bonds and their controlling forces.
TL;DR: The fundamental underpinnings of noncovalent bonds are presented, focusing on the σ-hole interactions that are closely related to the H-bond, with the introduction of a tetrel analog of the dihydrogen bond.
Journal ArticleDOI
Anion⋅⋅⋅Anion Interactions Involving σ-Holes of Perrhenate, Pertechnetate and Permanganate Anions.
TL;DR: In this article, the matere bond (MaB) was proposed to categorize these noncovalent interactions and differentiate them from the classical metal-ligand coordination bond.
Journal ArticleDOI
Anion⋅⋅⋅Anion Coinage Bonds: The Case of Tetrachloridoaurate
Andrea Daolio,Andrea Pizzi,Giancarlo Terraneo,Maurizio Ursini,Antonio Frontera,Giuseppe Resnati +5 more
TL;DR: In this paper, the distorted octahedral geometry of the bonding pattern around the gold center is rationalized on the basis of the anisotropic distribution of the electron density, which enables gold to behave as an electrophile (π-hole coinage-bond donor).
Journal ArticleDOI
On hydrogen bonds
TL;DR: The electrostatic nature of hydrogen bonds has been extensively studied in the literature as discussed by the authors, and it has been shown that the two dipoles will attract one another in the type of simple electrostatic dipole-dipole interaction we learned about earlier in class.
References
More filters
Journal ArticleDOI
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
Journal ArticleDOI
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
TL;DR: In this paper, a direct difference method for the computation of molecular interactions has been based on a bivariational transcorrelated treatment, together with special methods for the balancing of other errors.
Journal ArticleDOI
Multiwfn: a multifunctional wavefunction analyzer.
Tian Lu,Feiwu Chen +1 more
TL;DR: Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn, a multifunctional program for wavefunction analysis.
Journal ArticleDOI
Quantum mechanical continuum solvation models.
TL;DR: This paper presents a meta-modelling procedure called "Continuum Methods within MD and MC Simulations 3072", which automates the very labor-intensive and therefore time-heavy and expensive process of integrating discrete and continuous components into a discrete-time model.
Journal ArticleDOI
Note on an Approximation Treatment for Many-Electron Systems
Chr. Møller,Milton S. Plesset +1 more
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.