Intermolecular dispersion interactions of normal alkanes with rare gas atoms:: van der Waals complexes of n-pentane with helium, neon, and argon

Interaction energies of normal pentane with three rare gas atoms (helium, neon, and argon) were calculated using ab initio methods: the second-order Moller-Plesset (MP2), the fourth-order Moller-Plesset (MP4), and coupled cluster with single and double substitutions with noniterative triple excitation (CCSD(T)) levels of theory. Dunning's correlation consistent basis sets up to aug-cc-pVQZ were applied. Eight profiles (246 points for each rare gas atom) of potential energy surface (PES) of all-trans (anti-anti) conformation of n-pentane were scanned. Optimal distances for complex formation were found. MP2 interaction energies at the basis set limit were evaluated by three different methods (Feller's, Helgaker's, and Martin's). The MP2 interaction energy at the basis set limit for a global minimum of n-pentane complex with argon was more than 400cm(-1), so formation of a stable complex (at least at low temperature) can be expected. A comparison with previously published data on propane complexes with rare gas atoms (both computational and experimental) was done. The MP4 level of theory was found to be sufficient for a description of C5H12 complexes with helium, neon, and argon. (C) 2008 Elsevier B.V. All rights reserved.