Raman spectra of liquid and crystalline HCN and DCN

Abstract

Raman spectra of liquid and crystalline HCN and DCN have been recorded at various temperatures down to 77 OK. The spectra of the liquids are characteristic of hydrogen-bonded compounds. The two solid phases have very similar spectra, in which each fundamental is complicated by an anomalous shoulder on the high-frequency side. Possible explanations for these are given. Les deux phases solides prksentent dans chaque cas des spectres a peu pres identiques, oh chacune des fondamentales est compliqute par un Cpaulement du cbte des hautes frtquences. On suggere quelques explications pour ces anomalies.

Far-infrared and Raman Spectra of Crystalline ICN

“…Although the main features of the Raman spectrum of crystalline ICN are in agreement with the above predictions, it is clear that many of the fundamental bands are complicated by anomalous high-frequency shoulders, as was the case in HCN (8). The effect is slight in the C-N stretching (v,) region where only an asymmetry of the band is seen.…”

“…The only available Raman spectrum of cyanogen iodide was obtained with a photographic instrument, from a solution of ICN in methanol (7). Our main interest in this solid stemmed from the fact that it has a crystal structure somewhat similar to that of HCN, the Raman spectrum of which revealed anomalous dispersion on the high-frequency side of the fundamental bands (8). It has already been pointed out that such anomalies should occur in Raman spectra of non centro-symmetric crystals only (9).…”

A 1D Coordination Polymer of UF5 with HCN as a Ligand

“… Room temperature Raman spectrum of turquoise crystals of compound 1 under liquid HCN. The band at 2094 cm −1 is assigned to ν (C−N) of liquid HCN by comparison with the literature …”

A nuclear magnetic resonance relaxation study of liquid hydrogen cyanide

“…Many of the liquid state properties of HCN such as its unusually high dielectric constant are best interpreted in terms of the formation of linear polymeric hydrogen-bonded chains (2). 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).…”