What Types of Noncovalent Bonds Stabilize Dimers (XCP)2, for X = CN, Cl, F, and H?
Autor: | Janet E. Del Bene, Ibon Alkorta, José Elguero |
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Přispěvatelé: | Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Comunidad de Madrid |
Rok vydání: | 2019 |
Předmět: |
chemistry.chemical_classification
010304 chemical physics Hydrogen bond Chemistry Intermolecular force Binding energy Ab initio 010402 general chemistry 01 natural sciences Potential energy 0104 chemical sciences Crystallography 0103 physical sciences Halogen Potential energy surface Non-covalent interactions Physical and Theoretical Chemistry |
Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
ISSN: | 1520-5215 1089-5639 |
DOI: | 10.1021/acs.jpca.9b08141 |
Popis: | Ab initio MP2/aug′-cc-pVTZ calculations have been carried out in search of equilibrium dimers on (XCP) potential energy surfaces, for X = CN, Cl, F, and H. Five equilibrium dimers with D, C, C, C, and C symmetries exist on the (ClCP) potential energy surface, four on the (FCP) and (HCP) surfaces, and three on the (NCCP) surface. These dimers are stabilized by traditional halogen, pnicogen, and tetrel bonds, and one of them by a hydrogen bond. The binding energies of the dimers (XCP) vary from 3.0 to 22.0 kJ·mol, with the strongest and weakest bonds found for complexes on the (NCCP) surface. The binding energies of the linear D and C dimers on each surface differ by no more than 1.0 kJ·mol, except for (NCCP), which has D and C complexes with binding energies of 3.0 and 11.0 kJ·mol, respectively. The highly symmetric complexes with D and C symmetry are found on all surfaces and are the most weakly bound complexes on each surface. The structures of these dimers, the nature and strengths of charge-transfer interactions, the molecular graphs, and the molecular electrostatic potentials are useful for determining the type of intermolecular bond that stabilizes the dimers. EOM-CCSD spin-spin coupling constants J(P-P) for complexes with P···P pnicogen bonds and D symmetry are the largest coupling constants, ranging from 119 to 170 Hz. These increase with decreasing distance and follow a second-order trendline. The nature of the spin-spin coupling constants of these complexes is consistent with the type of noncovalent bond that stabilizes the dimers. This work was carried out with financial support from the Ministerio de Ciencia, Innovación y Universidades of Spain (PGC2018-094644-B-C22) and Comunidad Autónoma de Madrid (P2018/EMT-4329 AIRTEC-CM). Thanks are also given to the Ohio Supercomputer Center and CTI (CSIC) for their continued computational support |
Databáze: | OpenAIRE |
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