title: Furan-formic acid dimers: an ab initio and matrix isolation study.
abstract: The dimers formed by formic acid (FA) and furan are investigated by ab initio methods and matrix isolation spectroscopy. Nine complexes with binding energies between -3.91 and -0.82 kcal/mol (MP2/6-311++G(d,p) + ZPE + BSSE) are identified. Another five weaker bound complexes are localized at lower level of theory only. The binding in the furan-FA dimers can be described in terms of OH...O, C=O...H, HO...H, CH...O, OH...pi, and CH...pi interactions. Therefore, the furan-FA complexes are classified in two types: (1) the dimers where the OH hydrogen of formic acid interacts with the furan molecule and (2) the dimers where the main interactions of FA with the furan molecule are via the less acidic CH hydrogen. Duning's and Pople's triple and double basis sets were used to study the dependence of the geometries and energies of the complexes from the basis set. BSSE (basis set superposition error) counterpoise corrections (CP) were included during the geometry optimizations of all dimers at the MP2/6-31G(d,p) level of theory. Matrix isolation spectroscopy allowed us to record the IR spectrum of aggregates between FA and furan. By comparison of the experimental IR spectrum with calculated IR spectra of a variety of complexes, it was possible to identify the most stable furan-FA dimer as the major product of the aggregation.
authors.affiliation: Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, D-44780 Bochum, Germany.
authors.forename: Elsa
authors.initials: E
authors.lastname: Sánchez-García
authors.forename: Arthur
authors.initials: A
authors.lastname: Mardyukov
authors.forename: Marc
authors.initials: M
authors.lastname: Studentkowski
authors.forename: Luis A
authors.initials: LA
authors.lastname: Montero
authors.forename: Wolfram
authors.initials: W
authors.lastname: Sander
mesh_terms: D000465:Algorithms; D019281:Dimerization; D005561:Formates / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D006860:Hydrogen Bonding; D013057:Spectrum Analysis / Q000379:methods
chemical_list: D005561:Formates; D005663:Furans; C030544:formic acid; C039281:furan