A Systematic Approach to Identify Cooperatively Bound Homotrimers

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-01, Vol.117 (1), p.174-182
• Main Authors: Yang, Jack, Waller, Mark P
• Format: Article
• Language: English
• Subjects: Atomic and molecular clusters; Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Clusters; Computation; Crystal structure; Density-functional theory; Effects of atomic and molecular interactions on electronic structure; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Gas phases; Molecular solids; Multistage; Physical chemistry; Physics; Spectroscopy and geometrical structure of clusters; Studies of special atoms, molecules and their ions; clusters; Trimers
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp310067m

A systematic multistage computational procedure is presented to investigate cooperativity within trimeric molecular complexes. It is an alternative to exhaustive or stochastic-based approaches. Trimeric clusters were extracted from known crystal structures and optimized in the gas phase, and subsequently filtered using energetic and RMSD structural cutoffs. Three-body interaction energies were computed for the subset of distinct low-energy trimer conformations. The procedure was validated using a set of 20 molecular crystals taken from the Cambridge Structural Database, and 25% of these strucutres gave rise to gas-phase homotrimers that showed a cooperative binding energy at the BP86-D3(BJ)/def2-SVP//TPSS-D3(BJ)/def2-TZVP level of theory.