Spectroscopic investigations of hydrogen bonding interactions in the gas phase. II. The determination of the geometry and potential constants of the hydrogen-bonded heterodimer CH 3 CN • • • HF from its microwave rotational spectrum

1980 ◽  
Vol 370 (1741) ◽  
pp. 239-255 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Gas Phase ◽  
Spectroscopic Constants ◽  
Rotational Spectrum ◽  
Hydrogen Bonding Interactions ◽  
Isotopic Species ◽  
Microwave Rotational Spectrum ◽  
Vibration Rotation ◽  
Hydrogen Bonded

The microwave rotational spectrum of the hydrogen-bonded heterodimer CH 3 CN • • • HF has been identified and shown to be characteristic of a symmetric top. A detailed analysis of several rotational transitions for a variety of isotopic species gives the spectroscopic constants summarized in the following table: Rotational constants/MHz, vibration-rotation constants/MHz and vibrational separations/cm -1 of CH 3 CN • • • HF

Spectroscopic investigations of hydrogen bonding interactions in the gas phase. VIII. Microwave rotational spectrum of the heterodimer H—C≡C—C≡N ∙ ∙ ∙ HF

1984 ◽  
Vol 394 (1807) ◽  
pp. 387-403 ◽  
Keyword(s):  
Gas Phase ◽  
Continuous Wave ◽  
Spectroscopic Constants ◽  
State Transitions ◽  
Rotational Spectrum ◽  
Microwave Spectra ◽  
Hydrogen Bonding Interactions ◽  
Microwave Rotational Spectrum ◽  
Microwave Techniques ◽  
Pulsed Nozzle

The hydrogen bonded dimer formed between cyanoacetylene and hydrogen fluoride has been identified through its infrared and microwave spectra. Two microwave techniques, continuous wave and pulsed-nozzle Fourier-transform spectroscopy, have been combined to identify unambiguously the vibrational ground state transitions and to assign vibrational satellites. In making the assignments, much use has been made of computer simu­lation of spectra, which is described in an Appendix. Analysis of the microwave spectra led to the following spectroscopic constants and molecular parameters. HC 3 N ∙ ∙ ∙HF HC 3 N∙ ∙ ∙DF B 0 /MHz 1220.68431 (9) 1204.9051 (2) D J /kHz 0.306 (2) 0.296 (3) α β /MHz ─7.20 (2) — γ β /MHz 0.094 (3) — γ 11 /MHz ─0.030 (2) — α σ /MHz ─13.7 (2) — q β /MHz 3.12 (2) — r 0 (N ∙ ∙ ∙ F)/nm 0.2788 0.2785 X /MHz ─ 3.876 ─ 3.854 v β /cm -1 30 — v σ /cm -1 139 — k σ /(N m -1 ) 16.3 — k s /(N m -1 ) 770 — Finally, the variation of ∆ v̄ as a function of r 0 (N ∙ ∙ ∙ F) has been examined for a series of dimers RCN ∙ ∙ ∙ HF.

Erratum

1986 ◽  
Vol 404 (1826) ◽  
pp. 147-147 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Gas Phase ◽  
Ground State ◽  
Hyperfine Coupling ◽  
Rotational Spectrum ◽  
Centrifugal Distortion ◽  
Spectroscopic Investigations ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonded

Proc. R. Soc. Lond. A 401, 327-347 (1985) Spectroscopic investigations of hydrogen bonding interactions in the gas phase. X. Properties of the hydrogen-bonded heterodimer HCN⋯HF determined from hyperfine coupling and centrifugal distortion effects in its ground-state rotational spectrum By A. C. Legon, D. J. Millen and L. C. Willoughby On p. 327, at the end of the abstract, for 0.14 Å read 0.014 Å. On p. 343, line 7, for 0.025 Å read 0.014 Å. On p. 344, line 27, for 25.4° read 21.7°; line 33, for 6.6° read 2.9°. On p. 347, line 12, for 0.025 Å read 0.014 Å.

Spectroscopic investigations of hydrogen bonding interactions in the gas phase. IX. Vibrational satellites in the rotational spectrum of the hydrogen-bonded homodimer HCN • • • HCN

1985 ◽  
Vol 399 (1817) ◽  
pp. 377-390 ◽  
Keyword(s):  
Gas Phase ◽  
Ground State ◽  
Hydrogen Cyanide ◽  
Spectroscopic Constants ◽  
Rotational Spectrum ◽  
Optimum Conditions ◽  
Frequency Range ◽  
Hydrogen Bonding Interactions ◽  
Microwave Spectrometer ◽  
Simulation Of Spectra

The rotational spectrum of the hydrogen cyanide dimer has been observed in the frequency range 26-40 GHz by using a Stark-modulated microwave spectrometer. Although the spectrum is very weak, even under optimum conditions, it has been possible to assign vibrational satellites in the v β progression based on the ground state and in the v β progression based on v σ ═ 1 with the aid of the computer simulation of spectra and the ground-state spectroscopic constants. The spectroscopic constants now available for the hydrogen cyanide dimerare summarized as follows: (HC 14 N) 2 (DC 14 N) 2 (HC 15 N) 2 v β ═ 1 ← 0/cm -1 35±5 30±5 35±5 v σ ═ 1 ← 0/cm -1 101 ─ ─ B o /MHz 1745.80973(50) 1661.18(26) 1684.28825(25) D J /kHz 2.133(30) (1.873) 1.900(30) r c. m ./nm 44.496 ─ 44.499 K σ /(Nm -1 ) 8.14 ─ 8.51 α β /MHz ─20.07 (2) ─17.73 (27) ─18.74 (9) γ β /MHz 0.266 (4) 0.242 (36) 0.250 (17) q β /MHz 5.33 (4) 5.44 (13) 5.15 (10) α σ /MHz (31.44) ─ ─

Spectroscopic investigations of hydrogen bonding interactions in the gas phase. I. The determination of the geometry, dissociation energy, potential constants and electric dipole moment of the hydrogen-bonded heterodimer HCN • • • HF from its microwave rotational spectrum

1980 ◽  
Vol 370 (1741) ◽  
pp. 213-237 ◽  
Keyword(s):  
Dipole Moment ◽  
Electric Dipole Moment ◽  
Electric Dipole ◽  
Stark Effect ◽  
Potential Energy Function ◽  
Spectroscopic Constants ◽  
Rotational Spectrum ◽  
Energy Potential ◽  
Microwave Rotational Spectrum ◽  
Hydrogen Bonded

The microwave rotational spectrum of the hydrogen-bonded, linear heterodimer HCN • • • HF has been identified and a number of spectroscopic constants have been measured in a detailed analysis. The spectroscopic constants have been used in a variety of ways in order to evaluate parameters characterizing the potential energy function of the isolated dimer. An investigation of the Stark effect of two rotational transitions of HCN • • • HF has led to an accurate value of the electric dipole moment of the dimer and hence to the enhancement on dimer formation.

Spectroscopic investigations of hydrogen bonding interactions in the gas phase. III. The identification of the hydrogen-bonded heterodimer (CH 3 ) 3 CCN • • • HF and the determination of its geometry by microwave and infrared spectroscopy

1980 ◽  
Vol 370 (1741) ◽  
pp. 257-268 ◽  
Keyword(s):  
Hydrogen Bond ◽  
Symmetry Axis ◽  
Phase Iii ◽  
Rotational Constants ◽  
Hydrogen Bonding Interactions ◽  
Deuterium Substitution ◽  
Vibration Rotation ◽  
The One ◽  
Hydrogen Bonded

The existence of the hydrogen-bonded heterodimer (CH 3 ) 3 CCN • • • HF has been established from a study of its infrared and microwave spectra and from the latter the collinearity of the C—C = N • • • HF fragment has been demonstrated. Rotational constants for the ground state and the vibration-rotation constants α β and α σ for states associated with the hydrogen bond modes ν β (bending) and ν σ (stretching) are as follows for the species (CH 3 ) 3 CCN• • • HF and (CH 3 ) 3 CCN• • •DF: B 0 /MHz α σ /MNz α β /MNz (CH3)3CCN• • •HF 876.25 ± 0.12 12.3 ± 0.2 — 4.3 ± 0.1 (CH3)3CCN• • •DF 862.10 ± 0.09 12.4 ± 0.5 — 4.1 ± 0.1 From the intensity distribution within the v β satellite progression the value 55 + 5 cm -1 is determined for the vibrational separation v β =1 ← 0 ( v β is assumed harmonic). If monomer geometries are assumed unchanged on dimer formation the rotational constants B 0 lead to r 0 (N• • •F) = 2.725 ± 0.003 Å and 2.725 ± 0.003 Å for the hydrogen- and deuterium-bonded species respectively. It is thereby established that the N • • • F distance is on the one hand unaffected when D replaces H while on the other hand this distance progressively decreases in the series RCN • • • HF from 2.795 A when R = H, through 2.760 Å when R = CH 3 to 2·725 Å when R = (CH 3 ) 3 C. The latter conclusion provides an indication of increase of the strength of the hydrogen bond along the series. This is in agreement with the concomitant decrease of the force constants ƒ 8 (778, 744 and 736 N m -1 respectively) associated with the high frequency hydrogen motion along the symmetry axis as derived from the modified H—F stretching band in the infrared spectra of these dimers, and can be readily understood in terms of the inductive effect. The invariance of r 0 (N • • • F) to deuterium substitution is discussed in relation to the previous results on this topic and their interpretation.

Theoretical study of hydrogen bonding interactions in substituted nitroxide radicals

2021 ◽  
Author(s):  
Thufail M. Ismail ◽  
Neetha Mohan ◽  
P. K. Sajith
Keyword(s):  
Hydrogen Bonding ◽  
Interaction Energy ◽  
Electrostatic Potential ◽  
Molecular Electrostatic Potential ◽  
Theoretical Study ◽  
Nitroxide Radicals ◽  
Hydrogen Bonding Interactions ◽  
Bonded Complexes ◽  
Hydrogen Bonded

Interaction energy (Eint) of hydrogen bonded complexes of nitroxide radicals can be assessed in terms of the deepest minimum of molecular electrostatic potential (Vmin).

scholarly journals Hydrogen bonding interactions in single component molecular conductors based on metal (Ni, Au) bis(dithiolene) complexes

2020 ◽  
Vol 49 (18) ◽  
pp. 6056-6064 ◽  
Author(s):  
Hadi Hachem ◽  
Nathalie Bellec ◽  
Marc Fourmigué ◽  
Dominique Lorcy
Keyword(s):  
Hydrogen Bonding ◽  
Closed Shell ◽  
Single Component ◽  
Molecular Conductors ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonded

Nickel (closed-shell) or gold (radical) bis(dithiolene) neutral complexes, functionalized with hydroxyethyl and thiazole moieties, afford hydrogen-bonded single component conductors.

Sulfur as hydrogen-bond acceptor in cocrystals of 2-thio-modified thymine

2018 ◽  
Vol 74 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Wilhelm Maximilian Hützler ◽  
Michael Bolte
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Rational Design ◽  
Three Dimensional ◽  
Good Reliability ◽  
Hydrogen Bond Acceptor ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonding Site ◽  
Hydrogen Bonded

Doubly and triply hydrogen-bonded supramolecular synthons are of particular interest for the rational design of crystal and cocrystal structures in crystal engineering since they show a high robustness due to their high stability and good reliability. The compound 5-methyl-2-thiouracil (2-thiothymine) contains an ADA hydrogen-bonding site (A = acceptor and D = donor) if the S atom is considered as an acceptor. We report herein the results of cocrystallization experiments with the coformers 2,4-diaminopyrimidine, 2,4-diamino-6-phenyl-1,3,5-triazine, 6-amino-3H-isocytosine and melamine, which contain complementary DAD hydrogen-bonding sites and, therefore, should be capable of forming a mixed ADA–DAD N—H...S/N—H...N/N—H...O synthon (denoted synthon 3s N·S;N·N;N·O), consisting of three different hydrogen bonds with 5-methyl-2-thiouracil. The experiments yielded one cocrystal and five solvated cocrystals, namely 5-methyl-2-thiouracil–2,4-diaminopyrimidine (1/2), C5H6N2OS·2C4H6N4, (I), 5-methyl-2-thiouracil–2,4-diaminopyrimidine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C4H6N4·C3H7NO, (II), 5-methyl-2-thiouracil–2,4-diamino-6-phenyl-1,3,5-triazine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C9H9N5·C3H7NO, (III), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylformamide (2/2/1), (IV), 2C5H6N2OS·2C4H6N4O·C3H7NO, (IV), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylacetamide (2/2/1), 2C5H6N2OS·2C4H6N4O·C4H9NO, (V), and 5-methyl-2-thiouracil–melamine (3/2), 3C5H6N2OS·2C3H6N6, (VI). Synthon 3s N·S;N·N;N·O was formed in three structures in which two-dimensional hydrogen-bonded networks are observed, while doubly hydrogen-bonded interactions were formed instead in the remaining three cocrystals whereby three-dimensional networks are preferred. As desired, the S atoms are involved in hydrogen-bonding interactions in all six structures, thus illustrating the ability of sulfur to act as a hydrogen-bond acceptor and, therefore, its value for application in crystal engineering.

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