Car–Parrinello Molecular Dynamics Study of the Blue-Shifted F3CH⋅⋅⋅FCD3 System in Liquid N2

✍ Scribed by Pawel Rodziewicz; Konstanty S. Rutkowski; Sonia M. Melikova; Aleksander Koll; Francesco Buda

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 255 KB
• Volume: 7
• Category: Article
• ISSN: 1439-4235
• DOI: 10.1002/cphc.200600061

✦ Synopsis

Abstract

Fluoroform, as confirmed by both experimental and theoretical studies, can participate in improper H‐bond formation, which is characterized by a noticeable increase in the fundamental stretching frequency ν(CH) (so‐called blue frequency shift), an irregular change of its integral intensity, and a CH bond contraction. A Car–Parrinello molecular dynamics simulation was performed for a complex formed by fluoroform (F~3~CH) and deuterated methyl fluoride (FCD~3~) in liquid nitrogen. Vibrational analysis based on the Fourier transform of the dipole moment autocorrelation function reproduces the blue shift of the fundamental stretching frequency ν(CH) and the decrease in the integral intensity. The dynamic contraction of the CH bond is also predicted. The stoichiometry of the solvated, blue‐shifted complexes and their residence times are examined.