title: Glycolaldehyde monomer and oligomer equilibria in aqueous solution: comparing computational chemistry and NMR data.
abstract: A computational protocol utilizing density functional theory calculations, including Poisson-Boltzmann implicit solvent and free energy corrections, is applied to study the thermodynamic and kinetic energy landscape of glycolaldehyde in solution. Comparison is made to NMR measurements of dissolved glycolaldehyde, where the initial dimeric ring structure interconverts among several species before reaching equilibrium where the hydrated monomer is dominant. There is good agreement between computation and experiment for the concentrations of all species in solution at equilibrium, that is, the calculated relative free energies represent the system well. There is also relatively good agreement between the calculated activation barriers and the estimated rate constants for the hydration reaction. The computational approach also predicted that two of the trimers would have a small but appreciable equilibrium concentration (>0.005 M), and this was confirmed by NMR measurements. Our results suggest that while our computational protocol is reasonable and may be applied to quickly map the energy landscape of more complex reactions, knowledge of the caveats and potential errors in this approach need to be taken into account.
authors.affiliation: Department of Chemistry and Biochemistry, University of San Diego, 5998 Alcala Park, San Diego, California 92110, USA. jkua@sandiego.edu
authors.forename: Jeremy
authors.initials: J
authors.lastname: Kua
authors.forename: Melissa M
authors.initials: MM
authors.lastname: Galloway
authors.forename: Katherine D
authors.initials: KD
authors.lastname: Millage
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Avila
authors.forename: David O
authors.initials: DO
authors.lastname: De Haan
mesh_terms: D000079:Acetaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D003198:Computer Simulation; D019281:Dimerization; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D012996:Solutions; D013816:Thermodynamics; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D012996:Solutions; D014867:Water; D000079:Acetaldehyde; C010972:glycolaldehyde