How should we calculate multi-dimensional potential energy surfaces for an accurate reproduction of partition functions?

P. Vansteenkiste, V. Van Speybroeck, E. Pauwels, M. Waroquier
Chemical Physics
314 (1-3), 109-117


The potential energy of n-hexane is studied since it constitutes a typical example of a single chain molecule in which various internal rotations are present and a large number of conformations are existing, which cannot be reached by using one-dimensional rotational energy profiles. For an accurate reproduction of the global partition function and all derived thermodynamic properties an adequate description of all possible conformers is necessary. The full three-dimensional potential energy surface of the internal rotations in n-hexane (3D-PES) is calculated at an ab initio level and compared with one-dimensional schemes to reproduce the energy. Due to the higher dimensionality of the relevant potential energy surface, the computational cost is very high. A new approximate scheme based on two-dimensional cuts is proposed that gives good accuracy for the relative conformational energies and kinetic energies at a reasonable computational cost. This scheme is of general use for any long chain molecule.