Study on the cooperativity of hydrogen bonds betweenH₂YandHX(X=F,Cl,Br;Y=O,S,Se)

Abstract

The structure characteristics, interaction energies, cooperative energies of the complexes between chalcogen hydrides ( H 2 Y ) and halogen hydrides (HX) have been studied theoretically at the MP2 level with aug-cc-pVTZ basis set in this paper. The conclusions show that there are strong interactions between H 2 Y and HX. The stability of the complex is decided by the electronegativity of the negatively charged atom. The cooperativity is observed in the two or three hydrogen bonds of each trimer structures in title system. The values of the cooperative energies and the cooperative contributions all illustrate that the cooperativity is of great importance in these complexes. The "atoms in molecules" (AIM) analyses show that the complexes in title system are mainly electrostatic interactions (closed-shell interactions) in character. For H ⋯ O bonds in H 2 O ⋯ HF ⋯ H 2 O , H 2 O ⋯ HBr ⋯ H 2 O and HF ⋯ H 2 O ⋯ HF , the 1 < |Vc|/Gc < 2 and -Gc < Hc < 0 indicate the interactions in these compounds are between closed-shell interaction and opened-shell interaction.

Effect of substituents on complex stability and characteristics of Csp2‐H∙∙∙O/S and O/S‐H∙∙∙S/Se hydrogen bonds in the systems of monosubstituted selenoformaldehyde with H2O and H2S

“…Liu et al reported a similar trend that the HX•••nH2O was more stable than HX•••nH2S, with X = F, Cl, Br. [33] The result shows that the larger the electronegativity of the atoms is, the stronger the stability of the corresponding complex is. In this study, the much larger electronegativity of O in H2O as compared to S in H2S is the reason why the R-nO complexes are much more stable than R-nS ones.…”

“…Liu et al reached a similar conclusion on cooperative ability of HX•••2H2Z (X = F, Cl, Br; Z = O, S), in which the HX•••2H2O cooperative energy is much more negative than the HX•••2H2S ones. [33] Besides, substitution of H atom with the CH3 group leads to a stronger cooperative ability. In contrast, the cooperativity between the H-bonds is weaker when H atom is substituted by the halogen atoms.…”

Roles of H2O in comparison with H2S in the complexes of thioaldehydes and hydrogen chalcogenides

“…This result is consistent with the report of complexes HX•••nH2O/S (X = F, Cl, Br). [23] The interaction energies of R-1O are more than twice as many as R-1S, and the interaction energies of R-2O are triple as large as R-2S. Adding H2Z molecule to R-1Z (R = H, F, Cl, Br, CH3, and Z = O, S) causes an increase in the number of H-bonds, leading to a larger strength of complexes.…”

Femtochemistry of bimolecular reactions from weakly bound complexes: computational study of the H + H′OD → H′OH + D or HOD + H′ exchange reactions

“…The complex (HCl) [44][45][46] Fourier transform infrared (FTIR) spectroscopy in supersonic jets, 47,48 inert matrices [49][50][51][52][53][54] and Helium nanodroplets, [55][56][57] time-of-flight mass spectrometry and velocity-map imaging used to observe vibrational predissociation of the complex 58,59 and infrared cavity ringdown spectroscopy. 60,61 Many theoretical analyses using ab initio electronic structure methods [62][63][64][65][66][67][68][69][70][71][72][73][74][75][76] were published as well.…”