An ab initio study of the anionic clusters Cl–(HF)n (n = 1–5)

Nemukhin, Alexander V.; Granovsky, A. A.; Firsov, D. A.

doi:10.1070/mc1999v009n06abeh001153

Cited by 5 publications

(10 citation statements)

References 23 publications

(17 reference statements)

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“…Hydrogen bond energy for the complex FH···Cl − (not including zero‐point vibrational energy) is 22.06 kcal/mol, which compares well with the experimentally measured enthalpy of FH···Cl − formation . Previously similar calculated ΔE values of about 20–26 kcal/mol were reported . ΔE for n = 1 expectedly lies between experimental values of ΔE for [FHF] − (42 kcal/mol) and [ClHCl] − (14 kcal/mol).…”

Section: Resultssupporting

confidence: 84%

“…Geometric anticooperativity of FH···F − hydrogen bonds was studied computationally and experimentally by H/D isotope effects on 1 H and 19 F NMR chemical shifts . Apart of rather extensive literature on aqueous solutions of halide anions, other types of clusters of solvated negative ions are also discussed in literature—[(H 2 O) 2 Cl] − , [(H 2 O) 2 Br] − , [(H 2 O) 2 I] − , [(FH) n Cl] − , [(C 2 H 2 ) n Cl] − ( n = 1…9), [(C 2 H 2 ) n Br] − , [(C 2 H 2 ) n I] − , [(D 2 ) n Cl] − , [(D 2 ) n F] − , [(CH 4 ) n Cl] − , [(CH 4 ) n F] − , Cl − complexes with several CHCl 3 , CH 2 Cl 2 and CH 3 Cl molecules in crystal hydrates, and so forth.…”

Section: Introductionmentioning

confidence: 99%

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Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

2019

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The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH) nCl]− (n = 1…6) was calculated (CCSD/aug‐cc‐pVDZ) and compared with [(FH) nF]− clusters. The geometry is determined by the symmetry‐driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ‐hole), which limits the range of directions available for subsequent H‐bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H‐bonds by 23–16% and decreases their covalent character (as seen by LMO‐EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl. © 2019 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

2019

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“…This is consistent with the interaction energy of the above clusters. But for X Ϫ ⅐ (HX) 4,5 , where X ϭ F, Cl, Br, the delocalization values are found to increase with a decrease in the electronegativity of the halide ion. The actual DI values generally increase with the strength of the hydrogen bond; moreover, the value also depends on the nature of the proton donor [24].…”

Section: Topological Analysismentioning

confidence: 87%

“…For comparison, the neutral and anion clusters were also optimized at the second-order Møller-Plesset perturbation theory FIGURE 1. Structures of anion clusters of (a) (HX) 2 5 where X ϭ F, Cl, Br.…”

Section: Computational Detailsmentioning

confidence: 99%

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Density functional studies on hydrogen‐bonded clusters of hydrogen halides and the interaction on halide anions

Nirmala

Kolandaivel

2005

Int J of Quantum Chemistry

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Density functional theory (DFT) calculations have been performed to study the structures and stability of X Ϫ .(HX) nϭ2-5 clusters where X ϭ F, Cl, Br at B3LYP/6-311ϩϩG** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.

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Infrared Spectra and Ab Initio Calculations for the F^-−(CH₄)_n (n = 1−8) Anion Clusters

Loh¹,

Wilson²,

Wild³

et al. 2006

J. Phys. Chem. A

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Infrared spectra of mass-selected F- -(CH4)n (n = 1-8) clusters are recorded in the CH stretching region (2500-3100 cm-1). Spectra for the n = 1-3 clusters are interpreted with the aid of ab initio calculations at the MP2/6-311++G(2df 2p) level, which suggest that the CH4 ligands bind to F- by equivalent, linear hydrogen bonds. Anharmonic frequencies for CH4 and F--CH4 are determined using the vibrational self-consistent field method with second-order perturbation theory correction. The n = 1 complex is predicted to have a C3v structure with a single CH group hydrogen bonded to F-. Its spectrum exhibits a parallel band associated with a stretching vibration of the hydrogen-bonded CH group that is red-shifted by 380 cm-1 from the nu1 band of free CH4 and a perpendicular band associated with the asymmetric stretching motion of the nonbonded CH groups, slightly red-shifted from the nu3 band of free CH4. As n increases, additional vibrational bands appear as a result of Fermi resonances between the hydrogen-bonded CH stretching vibrational mode and the 2nu4 overtone and nu2+nu4 combination levels of the methane solvent molecules. For clusters with n < or = 8, it appears that the CH4 molecules are accommodated in the first solvation shell, each being attached to the F- anion by equivalent hydrogen bonds.

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An ab initio study of the anionic clusters Cl–(HF)n (n = 1–5)

Cited by 5 publications

References 23 publications

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Density functional studies on hydrogen‐bonded clusters of hydrogen halides and the interaction on halide anions

Infrared Spectra and Ab Initio Calculations for the F^-−(CH₄)_n (n = 1−8) Anion Clusters

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An ab initio study of the anionic clusters Cl–(HF)n (n = 1–5)

Cited by 5 publications

References 23 publications

Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

Density functional studies on hydrogen‐bonded clusters of hydrogen halides and the interaction on halide anions

Infrared Spectra and Ab Initio Calculations for the F-−(CH4)n (n = 1−8) Anion Clusters

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Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Infrared Spectra and Ab Initio Calculations for the F^-−(CH₄)_n (n = 1−8) Anion Clusters