The vibrational ground state rotational spectroscopic constants and structure of the HCN dimer

Buxton, L. W.; Campbell, E. J.; Flygare, W. H.

doi:10.1016/0301-0104(81)80161-9

Cited by 132 publications

(34 citation statements)

References 28 publications

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“…With D 0 ) 1.5 kcal/mol for the HCN dimer, we obtain a (N‚‚‚C) distance of 3.246 Å, a H-bond stretching frequency of 194 cm -1 , and an electronic H-bond energy D e ) 2.16 kcal/mol, which compare reasonably well with the experimental values of 3.287 Å, 120 cm -1 and 1.9 kcal/mol. 67,68 Thus, H-bonding in the HCN dimer is only slightly weaker than in the water dimer, and CN -must be extensively hydrogen bonded to water. Using D 0(C -HO) ) 4 kcal/mol for H-bond energy in the (NC -‚‚‚HOH) species, we obtain l C -O ) 2.94 Å and ω e(CO) ) 325 cm -1 .…”

Section: Introductionmentioning

confidence: 99%

Absolute Rate Calculations. Proton Transfers in Solution

2007

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The reaction path of the intersecting-state model is used in transition-state theory with the semiclassical correction for tunneling (ISM/scTST) to calculate the rates of proton-transfer reactions from hydrogen-bond energies, reaction energies, electrophilicity indices, bond lengths, and vibration frequencies of the reactive bonds. ISM/scTST calculations do not involve adjustable parameters. The calculated proton-transfer rates are within 1 order of magnitude of the experimental ones at room temperature, and cover very diverse systems, such as deprotonations of nitroalkanes, ketones, HCN, carboxylic acids, and excited naphthols. The calculated temperature dependencies and kinetic isotope effects are also in good agreement with the experimental data. These calculations elucidate the roles of the reaction energy, electrophilicity, structural parameters, hydrogen bonds, tunneling, and solvent in the reactivity of acids and bases. The efficiency of the method makes it possible to run absolute rate calculations through the Internet.

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Section: Introductionmentioning

confidence: 99%

Absolute Rate Calculations. Proton Transfers in Solution

2007

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“…This is not very different from the weak binding energy of the van der Waals dimer (3.99 kcal/mol). The calculated value of this binding energy is close to the calorimetric one of 3.28 kcal/mol (Giauque et al 1939) and the spectroscopic one (with our calculated zero-point energy correction) of 3.58 kcal/mol (Buxton et al 1981).…”

Section: Quantum Chemical Calculationsmentioning

confidence: 54%

The production of HCN dimer and more complex oligomers in dense interstellar clouds

Smith

Talbi

Herbst

2001

A&A

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Abstract. Using quantum chemical and kinetic techniques, we show that the reaction between two HCN molecules under interstellar conditions cannot lead efficiently to a dimer of this species (H2C2N2), whatever its structure. If the dimerization reaction does not occur efficiently, then it is impossible to synthesize detectable abundances of the pre-biotic HCN oligomer adenine (H5C5N5) in the interstellar medium via successive neutral-neutral reactions between HCN and its dimer, trimer, and tetramer.

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“…If one applies eq. [9] to any given molecule, r -is usually about 1% less than r l and this results in a 6% change in T~. However, in the case of a hydrogen-bonded liquid such as hydrogen cyanide there is no guarantee that the mean bond length in the liquid state will be the same as it is in the gas-phase monomer.…”

Section: Hydrogen Cyanidementioning

confidence: 99%

“…Indeed, such one-dimensional hydrogen-bonded chains are the dominant structural feature of the solid (3)(4)(5)(6). In the gas phase, the linear dimer is known to exist and its structure has recently been investigated using rotational microwave spectroscopy (7)(8)(9)(10).…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen cyanide is a particularly attractive molecule for nmr study because there are potentially five different stable nmr active isotopes: 'H, 'H, I3C, 14N, and I5N. Another advantage of HCN is that its structure is accurately known (3,(22)(23)(24)(25)(26) and, as well, a number of spectroscopic constants such as nuclear quadrupolar couplings (8,9,(22)(23)(24)(25)(26)(27)(28)(29), nuclear spin rotation constants (22,24,26,30), and chemical shielding anisotropies (31)(32)(33)(34)(35) are available. These constants are essential in the interpretation of the nmr relaxation data.…”

Section: Introductionmentioning

confidence: 99%

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A nuclear magnetic resonance relaxation study of liquid hydrogen cyanide

Wasylishen¹

1987

Can. J. Chem.

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RODER~CK E. WASYLISHEN. Can. J. Chem. 65, 2077Chem. 65, (1987. The rates of 'H, 13C, and ' 4~ spin-lattice relaxation for liquid deuterium cyanide have been studied as a function of temperature. The quadrupolar nuclei relax exclusively by the quadrupolar relaxation mechanism while the rate of I3C and "N relaxation is completely dominated by the spin-rotation mechanism. The apparent activation energy that describes the temperature dependence of spin-lattice relaxation for all nuclei studied is approximately 1.6 kcal mol-I. The temperature dependence of the rate of I3C relaxation in liquid HCN was also investigated. Although the determination of very accurate rotational and angular momentum correlation times is hampered by intermolecular effects on the nuclear quadrupolar coupling constants and the appropriately averaged C-H bond separation, the derived correlation times for DCN and HCN are in reasonable agreement ( '-15%).RODERICK E. WASYLISHEN. Can. J. Chem. 65, 2077Chem. 65, (1987. On a ttudit les vitesses de relaxation spin-rkseau 'H, I3C et 1 4~ du cyanure de deutCrium liquide, a diverses tempkratures. Le mecanisme de relaxation du noyau quadrupolaire n'implique qu'une relaxation quadrupolaire alors que la vitesse de relaxation du 13C et du ' 4~ est complktement dominCe par un mtcanisme spin-rotation. L'Cnergie d'activation apparente qui dCcrit la relation entre la tempkrature et la relaxation spin-rCseau de chacun des noyaux CtudiCs est d'environ 1,6 kcal mol-l. On a aussi CtudiC la relation entre la temperature et la vitesse de relaxation du 13C, dans le HCN liquide. MCme si la determination de valeurs trks precises pour les temps de corrtlation des moments rotationnel et angulaire est rendue difficile par les effets intermolCculaires sur les constantes de couplages nuclCaires quadrupolaires et par la sCparation de la liaison C-H qui est approximativement moyenne, on obtient un accord raisonnable ( k 15%) pour les temps de corrClation que l'on a d6rivC pour le DCN et le HCN.[Traduit par la revue] Introduction At atmospheric pressure hydrogen cyanide, HCN, exists as a liquid over a relatively narrow temperature range, 39 degrees

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The vibrational ground state rotational spectroscopic constants and structure of the HCN dimer

Cited by 132 publications

References 28 publications

Absolute Rate Calculations. Proton Transfers in Solution

Absolute Rate Calculations. Proton Transfers in Solution

The production of HCN dimer and more complex oligomers in dense interstellar clouds

A nuclear magnetic resonance relaxation study of liquid hydrogen cyanide

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