Ab initiostudies on structure, vibrational spectra and infrared intensities of HCN, (HCN)2and (HCN)3

Kofranek, Manfred; Lischka, Hans; Karpfen, Alfred

doi:10.1080/00268978700101961

Cited by 58 publications

(33 citation statements)

References 60 publications

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“…These derivatives were previously evaluated (14) by means of a one-dimensional Chebyshev polynomial fitting of the H-bonded stretching coordinate R, using the frozen monomer geometry approach (FMG). It is seen that the FMG fitted derivatives are noticeably exaggerated and the present results, using the fully optimised geometry approach (FOG), are in satisfactory agreement with the experimental values available as well as with the ab initio calculations reported by Kofranek et al (23). It is also noted that the dipole derivatives for the proton-donor C-H mode in the HCN trimer are considerably larger than the respective values for the free monomer unit.…”

Section: Resultssupporting

confidence: 77%

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Mechanical and electrical anharmonicities of the linear hydrogen cyanide H-bonded trimer

Almeida¹

1991

Can. J. Chem.

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WAGNER B. DE ALMEIDA. Can. J . Chem. 69,2044Chem. 69, (1991. The anharmonicity of the hydrogen-bonded (N.. .H) and proton-donor (C-H) stretching modes of the linear (HCN)3 species are calculated at the SCF level with the 4-3 1G and 6-31G** basis sets. Third and fourth energy derivatives and second and third dipole moment derivatives, which are needed to calculate the anharmonic terms, were evaluated by means of the one-dimensional Chebyshev polynomial fitting to the calculated ab initio points. Frequencies and intensities of overtone bands are reported and the effect of geometry relaxation on the polynomial fitted derivatives as well as mechanical anharmonicity on the vibrational intensities discussed.

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Section: Resultssupporting

confidence: 77%

“…The present intensities of the fundamental band appear to be satisfactorily represented. The deviations from the values reported by Kofranek et al (23) including electron correlation at the CPF (Coupled Pair Functional approach) level can be attributed to the small basis set employed rather than the methodology applied here.…”

Section: Resultscontrasting

confidence: 45%

Mechanical and electrical anharmonicities of the linear hydrogen cyanide H-bonded trimer

Almeida¹

1991

Can. J. Chem.

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“…The HCN dimer has been the subject of numerous experimental [8][9][10][11][12][13][14][15][16][17] and theoretical [18][19][20][21][22][23] studies, in both the gas phase and in matrices. While rotational resolution is available in both the microwave 8,9 and infrared [13][14][15][16] gas phase studies, the broadening associated with the inhomogeneous environment in a cold, solid matrix results in broad vibrational bands that mask the dynamics.…”

Section: Introductionmentioning

confidence: 99%

“…As a result it can bend significantly, as indicated by its low bending frequency. 14,15,19 Considerable attention has also been directed towards the vibrational predissociation dynamics of this dimer. The energies associated with intramolecular vibrations of a weakly bound complex are often sufficient to dissociate the weak intermolecular bond.…”

Section: Introductionmentioning

confidence: 99%

Solvent mediated vibrational relaxation: Superfluid helium droplet spectroscopy of HCN dimer

Nauta

Miller

1999

The Journal of Chemical Physics

120

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Articles you may be interested inInfrared spectroscopy of HOCl embedded in superfluid helium nanodroplets: Probing the dynamical response of the solvent J. Chem. Phys. 137, 014302 (2012); 10.1063/1.4731283 Near-infrared spectroscopy of ethylene and ethylene dimer in superfluid helium dropletsRotationally resolved infrared spectra are reported for the HCN dimer, grown and solvated in liquid helium droplets. This is the first study for which two different vibrational modes within the same liquid helium solvated molecule have been observed, namely those associated with the ''free'' and the ''hydrogen-bonded'' C-H stretching vibrations. Comparing the line broadening in these two bands, we conclude that the helium solvent plays an important role in the vibrational relaxation dynamics of the dimer. The rotational constants obtained from these spectra indicate that the dimer rotates more slowly in the liquid than in the gas phase.

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“…The standard enthalpy of formation was determined from the temperature dependent intensities of the absorption bands of the monomer and dimer to be ⌬H D 0 ϭϪ(23.85Ϯ2.10)kJ mol Ϫ1 ͑see Concerning the structure and the dipole moment of (HCN) 2 we can rely on numerous experimental and theoretical investigations. Legon, Millen, and Mjöberg 42 have determined the rotational constant of the dimer in the gas phase Ab initio calculations on a linear HCN dimer done by Kofranek et al 45,46 yield a dipole moment between 6.57 and 7.37 D. The equilibrium bond length r 0 ͑N¯C͒ lies between 3.33 and 3.40 Å. The enthalpy of dimerization varies between Ϫ14.2 and Ϫ15.9 kJ mol Ϫ1 .…”

Section: The Formation and Properties Of Hcn Dimersmentioning

confidence: 99%

Electron and anion mobility in low density hydrogen cyanide gas. I. Dipole-bound electron ground states

Klahn

Krebs

1998

The Journal of Chemical Physics

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Erratum: "Electron and anion mobility in low density hydrogen cyanide gas. I. Dipole-bound electron ground states" [J.Electron and anion mobility in low density hydrogen cyanide gas. I. Dipole-bound electron ground states Electron and anion mobility in low density hydrogen cyanide gas. II. Evidence for the formation of anionic clusters Negative ion photoelectron spectroscopy of the ground state, dipole-bound dimeric anion, ( HF ) 2 − We measured the mobility of excess electrons in the polar hydrogen cyanide gas (Dϭ2.985 D͒ at low densities as a function of density and temperature by the so-called pulsed Townsend method. Experiments were performed at 294 and 333 K in the gas number density range 1.23ϫ10 17 рn р3.61ϫ10 18 cm Ϫ3 . We found a strong density dependence of the ''zero-field'' density-normalized mobility (n). Only about 10% of the observed density variation can be qualitatively explained by coherent and incoherent multiple scattering effects. With increasing gas density an increasing number of linear HCN dimers is formed which due to the high dipole moment (Dϭ6.552 D͒ represent much stronger electron scatterers than the HCN monomers. It was found that the dimers may be only in part responsible for the observed density effect. Therefore, we consider a transport process where short-lived dipole-bound electron ground states ͑lifetime у12 ps͒ as quasilocalized states are involved. For comparison the electron mobility in saturated 2-aminoethanol vapor with a dipole moment of similar size (Dϭ3.05 D͒ does not show any anomalous density behavior in the temperature range 298рTр435 K. In contrast to this the electron mobility in saturated but also in nonsaturated CH 3 CN gas (Dϭ3.925 D͒ shows a density behavior similar to that in HCN.

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Ab initiostudies on structure, vibrational spectra and infrared intensities of HCN, (HCN)₂and (HCN)₃

Cited by 58 publications

References 60 publications

Mechanical and electrical anharmonicities of the linear hydrogen cyanide H-bonded trimer

Mechanical and electrical anharmonicities of the linear hydrogen cyanide H-bonded trimer

Solvent mediated vibrational relaxation: Superfluid helium droplet spectroscopy of HCN dimer

Electron and anion mobility in low density hydrogen cyanide gas. I. Dipole-bound electron ground states

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