Secondary Interaction Contribution in Hydrogen-Bonded Complex: Theoretical Model Study in Hydrogen Fluoride Trimer

The hydrogen bonded heterodimer formed between oxirane and hydrogen fluoride has been identified through its infrared and microwave spectra. Rotational constants/MHz and centrifugal distortion constants/kHz for the following isotopic varieties have been derived from an analysis of the rotational spectra in the vibrational ground state: A B A (CH 2 ) 2 160* • -HF 16099 3638.75 3462.31 15.3 25.8 (CH2)2160- • *DF 15984 3605.66 3434.85 14.1 20.9 For the species (CH2)2180 • • • HF only the rotational constants 7059.7 MHz and B — C = 135 MHz could be obtained. It is established from arguments based on Pband A that the dimer has a pyramidal configuration at the oxygen atom and that the molecular point group is (7g. If the justifiable assumption is made that the monomer geometries are unchanged on dimer formation, then the observed rotational constants for (CH 2 )2160* • -H F leadtor0(O* • *F) = 2.627 A ja n d ^ = 71.8°, where ^ is the angle between the plane of the three-membered ring and the H—F direction. Replacement of H by D in the hydrogen bond does not significantly change these values.

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Controlling the conductance of molecular junctions using proton transfer reactions: A theoretical model study

The Journal of Chemical Physics ◽

10.1063/1.4974512 ◽

2017 ◽

Vol 146 (9) ◽

pp. 092317 ◽

Cited By ~ 9

Author(s):

Chriszandro Hofmeister ◽

Pedro B. Coto ◽

Michael Thoss

Keyword(s):

Theoretical Model ◽

Proton Transfer ◽

Molecular Junctions ◽

Transfer Reactions ◽

Model Study ◽

Proton Transfer Reactions

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One-proton and multiproton hydrogen bonds between ammonium ions and hydrogen fluoride

Canadian Journal of Chemistry ◽

10.1139/v85-265 ◽

1985 ◽

Vol 63 (7) ◽

pp. 1562-1567 ◽

Cited By ~ 4

Author(s):

Henryk T. Flakus ◽

Russell J. Boyd

Keyword(s):

Hydrogen Fluoride ◽

Electron Correlation ◽

Basis Set ◽

Molecular Orbital Calculations ◽

Correlation Effects ◽

Ammonium Ions ◽

Electron Correlation Effects ◽

The One ◽

Bonded Complexes ◽

Hydrogen Bonded

Extensive abinitio molecular orbital calculations are reported for the hydrogen bonded complexes of the formula [Formula: see text] and, [Formula: see text] where m = 0, 1, 2, and 3. The one-proton ("linear") hydrogen bonded complexes of the ammonium ions and hydrogen fluoride are predicted to be more stable by about 1 or 2 kcal/mol than the two- and three-proton ("bent") complexes. Several systematic trends and a number of differences between the neutral and protonated series of complexes are observed. The basis set dependence of the results, basis set superposition errors and electron correlation effects are discussed.

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Electric field assisted hydrogen fluoride etching of silica

Proceedings of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rspa.2009.0216 ◽

2009 ◽

Vol 465 (2111) ◽

pp. 3447-3462 ◽

Cited By ~ 1

Author(s):

Ruy Batista Santiago Neto ◽

Bernhard Lesche

Keyword(s):

Theoretical Model ◽

Electric Field ◽

Electric Fields ◽

Chemical Reaction ◽

Hydrogen Fluoride ◽

Critical Analysis ◽

Mean Field ◽

Nonlinear Effects ◽

Dipole Orientation ◽

Field Screening

The influence of electric fields on the velocity of the chemical reaction 4HF+SiO 2 →SiF 4 +2H 2 O in aqueous solution is investigated experimentally. The field strengths used were high enough to measure nonlinear effects. The results permit a critical analysis of a theoretical model known in literature. The basic idea of dipole orientation changing the rate of the primary step of the chemical reaction can explain the experimental data, but several important details of the original model had to be changed. The primary step involves two hydrogen fluoride (HF) molecules rather than one, and field screening by mobile ions has a significant influence causing nonlinear effects. The fact that field screening plays an important role implies that electric field-assisted HF etching of silica may by used as an instrument for measuring ion concentrations in highly concentrated electrolytes. The data measured may be well described by a theoretical model based on mean field approximations. The results give an insight into the structure of highly concentrated hydrofluoric acid and also permit a critical analysis of applications of the effect in measuring electric fields written in glass samples by electrothermal poling. The effect may also be used for shaping glass surfaces.

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