The Random Phase Approximation (RPA), unlike other Density Functional Theory (DFT) based methods, naturally takes into account some dispersion interaction. It can be shown that in the limit of large separation RPA exactly reproduces the dispersion interaction between two molecules. But how this approximation translates to intramolecular interactions and host-guest interaction energy in real systems requires some investigation. To help answer this question, we compare RPA calculated interaction energies for a test set1 of pairs of large, highly conjugated hosts and guests to experiment. To characterize intramolecular interaction we calculate the rotational constants of a set2 of organic molecules. 1. Benchmarking of London Dispersion-Accounting Density Functional Theory Methods on Very Large Molecular Complexes Tobias Risthaus and Stefan Grimme Journal of Chemical Theory and Computation 2013 9 (3), 1580-1591 DOI: 10.1021/ct301081n 2. Implementation of nuclear gradients of range-separated hybrid density functionals and benchmarking on rotational constants for organic molecules Tobias Risthaus, Marc Steinmetz and Stefan Grimme Journal of Computational Chemistry 2014 35 (20), 1509–1516 DOI: 10.1002/jcc.23649

Benchmarking the random-phase approximation

251st National Meeting (2016)

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