Nature of Alkali- and Coinage-Metal Bonds Versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A-M and B- in archetypal [A-M center dot center dot center dot B](-) model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density funct...

Descripción completa

Detalles Bibliográficos
Autores: Larrañaga Agirre, Olatz, Arrieta Ayestaran, Ana Jesús, Fonseca Guerra, ‪Célia, Bickelhaupt, F. Matthias, De Cózar Ruano, Abel
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/50574
Acceso en línea:http://hdl.handle.net/10810/50574
Access Level:acceso abierto
Palabra clave:activation strain model
bond theory
DFT calculations
hydrogen bonding
metal bonding
molecular-orbital theory
charge-transfer
halogen bonds
lithium bond
base-pairs
energy
approximation
noncovalent
Descripción
Sumario:We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A-M and B- in archetypal [A-M center dot center dot center dot B](-) model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A-M and B- using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.