Bork, Nicolai Christian4; Du, Lin4; Reiman, Heidi3; Kurtén, Theo3; Kjærgaard, Henrik Grum5
1 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet2 Department of Chemistry, Faculty of Science, Københavns Universitet3 University of Helsinki4 Department of Chemistry, Faculty of Science, Københavns Universitet5 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet
Models of formation and growth of atmospheric aerosols are highly dependent on accurate cluster binding energies. These are most often calculated by ab initio electronic structure methods but remain associated with significant uncertainties. We present a computational benchmarking study of the Gibbs free binding energies in molecular complexes and clusters based on gas phase FTIR spectroscopy. The acetonitrile-HCl molecular complex is identified via its redshifted H-Cl stretching vibrational mode. We determine the Gibbs free binding energy, ΔG°295 K, to between 4.8 and 7.9 kJ mol(-1) and compare this range to predictions from several widely used electronic structure methods, including five density functionals, Møller-Plesset perturbation theory, and five coupled cluster methods up to CCSDT quality, considering also the D3 dispersion correctional scheme. With some exceptions, we find that most electronic structure methods overestimate ΔG°295 K. The effects of vibrational anharmonicity is approximated using scaling factors, reducing ΔG°295 K by ca. 1.8 kJ mol(-1), whereby ΔG°295 K predictions well within the experimental range can be obtained.
Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophysical, 2014, Vol 118, Issue 28, p. 5316-5322