Intermolecular Hydrogen Bonding and Vibrational Analysis of N,N-Dimethylformamide Hexamer Cluster

Abstract

Hexamer cluster of N,N-dimethylformamide(DMF) based on the crystal structure was investigated for the equilibrium structure, the stabilization energies, and the vibrational properties in the density functional force field. The geometry (point group <TEX>$C_i$</TEX>) of fully optimized hexamer clustered DMF shows quite close similarity to the crystal structure weakly intermolecular hydrogen bonded each other. Stretching force constants for intermolecular hydrogen bonded methyl and formyl hydrogen atoms with nearby oxygen atom, methyl C–H<TEX>${\cdots}$</TEX>O and formyl C–H<TEX>${\cdots}$</TEX>O, were obtained in 0.055 <TEX>$\sim$</TEX> 0.11 and <TEX>$\sim$</TEX> 0.081 mdyn/<TEX>$\AA$</TEX>, respectively. In-plane bending force constants for hydrogen bonded methyl hydrogen atoms were in 0.25 <TEX>$\sim$</TEX> 0.33, and for formyl hydrogen <TEX>$\sim$</TEX> 0.55 mdynÅ. Torsion force constants through hydrogen bonding for methyl hydrogen atoms were in 0.038 <TEX>$\sim$</TEX> 0.089, and for formyl hydrogen atom <TEX>$\sim$</TEX> 0.095 mdynÅ. Calculated Raman and infrared spectral features of single and hexamer cluster represent well the experimental spectra of DMF obtained in the liquid state. Noncoincidence between IR and Raman frequency positions of stretching C=O, formyl C–H and other several modes was interpreted in terms of the intermolecular vibrational coupling in the condensed phase.