title: Molecular structure, vibrational spectroscopic, hyperpolarizability, natural bond orbital analysis, frontier molecular orbital analysis and thermodynamic properties of 2,3,4,5,6-pentafluorophenylacetic acid.
abstract: The FT-IR (4000-400cm(-)(1)) and FT-Raman spectra (3500-100cm(-)(1)) of 2,3,4,5,6-pentafluorophenylacetic acid (PAA) have been recorded. Density functional theory calculation with LSDA/6-31+G(d,p) and B3LYP/6-31+G(d,p) basis sets have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman intensities and bonding features of the title compound. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of PAA are calculated using B3LYP/6-31+G(d,p) method on the finite-field approach. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The stability of molecule has been analyzed by using NBO analysis. The calculated HOMO and LUMO energies show that charge transfer occurs within this molecule. Mulliken population analysis on atomic charges is also calculated. Thermodynamic properties (heat capacity, enthalpy, Gibb's free energy and entropy) of the title compound at different temperatures were calculated.
authors.affiliation: Centre for Research, Department of Physics, AA Government Arts College, Musiri 621 211, India. Electronic address: brsbala@rediffmail.com.
authors.forename: V
authors.initials: V
authors.lastname: Balachandran
authors.affiliation: PG and Research Department of Physics, Government Arts College, Ariyalur 621 713, India.
authors.forename: V
authors.initials: V
authors.lastname: Karunakaran
mesh_terms: D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010648:Phenylacetates / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics
chemical_list: D006845:Hydrocarbons, Fluorinated; D010648:Phenylacetates
keywords: 2,3,4,5,6-Pentafluorophenylacetic acid; DFT calculations; First hyperpolarizability; HOMO and LUMO; Vibrational spectra