title: Raman and DFT study of polar nu(CN) and non-polar nu(C-H) modes of acetonitrile in aqueous Ag nano-colloids.
abstract: Raman spectra of acetonitrile (Acn) in different millimolar (mM) concentrations adsorbed on Ag nano-colloids were recorded in the region 2100-3300cm(-1). The nu(CN) and nu(C-H) modes show blue shifts of approximately 3 and approximately 1cm(-1), respectively, when the concentration of Acn in the mixture is increased from 2 to 8mM. The blue shift of nu(CN) and nu(C-H) modes is predominantly because of adsorption of Acn molecules on Ag nano-colloids. The wave number shift and variation of intensity of the nu(CN) and nu(C-H) bands have been discussed in terms of the adsorption geometry, which probably changes from flat-on configuration at lower concentration of Acn to an end-on configuration at higher concentration of Acn. The dephasing of nu(CN) oscillator becomes considerably slower at higher concentration of Acn. The adsorption of Acn molecules on the nano-colloids was simulated using the (B3LYP) method and the basis sets used for Acn molecules and Ag atoms were 6-311++G(d,p) and Lanl2dz, respectively.
authors.affiliation: Department of Physics, Banaras Hindu University, Varanasi, Uttar Pradesh , India.
authors.forename: Shivangi
authors.initials: S
authors.lastname: Mishra
authors.forename: Dheeraj K
authors.initials: DK
authors.lastname: Singh
authors.forename: Animesh K
authors.initials: AK
authors.lastname: Ojha
authors.forename: B P
authors.initials: BP
authors.lastname: Asthana
authors.forename: Ranjan K
authors.initials: RK
authors.lastname: Singh
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000327:Adsorption; D003102:Colloids / Q000737:chemistry; D053768:Metal Nanoparticles / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D014867:Water
chemical_list: D000097:Acetonitriles; D003102:Colloids; D014867:Water; D012834:Silver; C032159:acetonitrile