title: Stochastic Search of Molecular Cluster Interaction Energy Surfaces with Coupled Cluster Quality Prediction. The Phenylacetylene Dimer.
abstract: We report a stochastic search methodology on the basis of dispersion-augmented density functional theory (DFT), aimed at finding low energy isomers of the phenylacetylene dimer as well as methane and benzene dimers. Stochastic search of the molecular cluster interaction energy surfaces was carried out with the computationally inexpensive dispersion-augmented, third-order self-consistent charge density functional tight-binding (DFTB3-D) method, and energetically low-lying molecular cluster geometries were identified, including several that had previously been optimized at the MP2/cc-pVTZ level of theory and had single point interaction energies evaluated at the coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) level of theory in the complete basis set limit (Maity, S. et al. Phys. Chem. Chem. Phys 2011, 13, 16706). In addition, the search procedure identifies several additional low-energy isomers that map a reaction path, rotating one monomer through a full 360° relative to the first. We found that binding energies from long-range corrected functional combined with the local response dispersion correction (LC-BOP+LRD) yields binding energies that are within 1 kJ mol(-1) of the CCSD(T)/CBS results for both π-stacked and CH···π structures. In contrast, other functionals and second-order Møller-Plesset perturbation methods favored one binding motif or the other and therefore are not ideal to describe a global potential energy surface.
authors.affiliation: Department of Chemistry, Nagoya University , Furo-cho, Chikusa-ku Nagoya 464-4602, Japan.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Addicoat
authors.affiliation: Department of Chemistry, Nagoya University , Furo-cho, Chikusa-ku Nagoya 464-4602, Japan.
authors.forename: Yoshifumi
authors.initials: Y
authors.lastname: Nishimura
authors.affiliation: Photon Science Center, University of Tokyo , Tokyo 113-8656, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Sato
authors.affiliation: Fuel Cell Nanomaterials Center, University of Yamanashi , Kofu 400-0021, Japan.
authors.forename: Takao
authors.initials: T
authors.lastname: Tsuneda
authors.affiliation: Department of Chemistry, Nagoya University , Furo-cho, Chikusa-ku Nagoya 464-4602, Japan.
authors.forename: Stephan
authors.initials: S
authors.lastname: Irle