title: An Empirical IR Frequency Map for Ester C═O Stretching Vibrations.
abstract: We present an approach for parametrizing spectroscopic maps of carbonyl groups against experimental IR absorption spectra. The model correlates electric fields sampled from molecular dynamics simulations with vibrational frequencies and line shapes in different solvents. We perform an exhaustive search of parameter combinations and optimize the parameter values for the ester carbonyl stretching mode in ethyl acetate by comparing to experimental FTIR spectra of the small molecule in eight different solvents of varying polarities. Hydrogen-bonding solvents require that the peaks are fit independently for each hydrogen bond ensemble to compensate for improper sampling in molecular dynamics simulations. Spectra simulated using the optimized electrostatic map reproduce C═O IR absorption spectra of ethyl acetate with a line center RMSD error of 4.9 cm(-1) over 12 different solvents whose measured line centers span a 45 cm(-1) range. In combination with molecular dynamics simulations, this spectroscopic map will be useful in interpreting spectra of ester groups in heterogeneous environments such as lipid membranes.
authors.affiliation: Department of Chemistry, University of Texas at Austin , 105 E. 24th St. Stop A5300, Austin, Texas 78712-1224, United States.
authors.forename: Sean C
authors.initials: SC
authors.lastname: Edington
authors.affiliation: Department of Chemistry, University of Texas at Austin , 105 E. 24th St. Stop A5300, Austin, Texas 78712-1224, United States.
authors.forename: Jennifer C
authors.initials: JC
authors.lastname: Flanagan
authors.affiliation: Department of Chemistry, University of Texas at Austin , 105 E. 24th St. Stop A5300, Austin, Texas 78712-1224, United States.
authors.forename: Carlos R
authors.initials: CR
authors.lastname: Baiz
mesh_terms: D002244:Carbon / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D010100:Oxygen / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D055672:Static Electricity
chemical_list: D004952:Esters; D012997:Solvents; D002244:Carbon; D010100:Oxygen