The interplay and strength of the π⋯HF, C⋯HF, F⋯HF and F⋯HC hydrogen bonds upon the formation of multimolecular complexes based on C2H2⋯HF and C2H4⋯HF small dimers

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 213; pp. 438 - 455
• Main Authors: Carvalho, Leila Cardoso, Bueno, Mauro Alves, de Oliveira, Boaz Galdino
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.04.2019
• Subjects: Acetylene; B3LYP; ChelpG; Ethylene; Hydrogen bonds; NBO; QTAIM; Hydrogen bonds; Ethylene; B3LYP; NBO; QTAIM; ChelpG; Acetylene
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2019.01.004

The conception of this theoretical research was idealized aiming to unveil the intermolecular structures of complexes formed by acetylene or ethylene and hydrofluoric acid. At light of computational calculations by using the B3LYP/6-311++G(d,p) method, the geometries of the C2H2⋯(HF), C2H2⋯2(HF), C2H2⋯4(HF), C2H4⋯(HF), C2H4⋯2(HF) and C2H4⋯4(HF) hydrogen-bonded complexes were fully optimized. Moreover, the Post-Hartree-Fock calculations MP2/6-311++G(d,p), MP2/aug-cc-pVTZ, MP4(SDQ)/6-311++G(d,p) and CCSD/6-311++G(d,p) also were also used. The infrared spectra were analyzed in order to identify the new vibrational modes and frequencies of the proton donors shifted to red region. Through the modeling of charge-fluxes on the basis of the Quantum Theory of Atoms In Molecules (QTAIM) and, by contradicting the expectation of the hydrofluorination mechanisms of acetylene or ethylene, C⋯HF was recognized as a new type of hydrogen bond instead of the already well known π⋯H. The calculations of the Natural Bonding Orbital (NBO) and Charges derived from the Electrostatic Potential Grid-based (ChElPG) were also applied to interpret the shifting frequencies as well as measuring of the punctual charge-transfer after the formation of the complexes. Finally, the determination of the stabilization energy was carried out through the arguments of the Fock matrix in NBO basis and through the supermolecule approach. Also it is worthwhile to notice that some algebraic formulations were used for determining the electronic cooperative effect (CE). [Display omitted] •DFT and ab initio calculations were used for computing hydrogen bond properties.•The occurrence of π⋯H hydrogen bond in complexes formed by acetylene and ethylene•The QTAIM, NBO, ChElPG approaches were used to justify the infrared spectrum effects.•The interaction strength and the cooperativity effect were measured in order to understand the intermolecular stability.