Obtaining the lattice energy of the anthracene crystal by modern yet affordable first-principles methods

The non-covalent interactions in organic molecules are known to drive their self-assembly to form molecular crystals. We compare, in the case of anthracene and against experimental (electronic-only) sublimation energy, how modern quantum-chemical methods are able to calculate this cohesive energy taking into account all the interactions between occurring dimers in both first-and second-shells. These include both O(N 6)- and O(N 5)-scaling methods, Local Pair Natural Orbital-parameterized Coupled-Cluster Single and Double, and Spin-Component-Scaled-Møller-Plesset perturbation theory at second-order, respectively, as well as the most modern family of conceived density functionals: double-hybrid expressions in several variants (B2-PLYP, mPW2-PLYP, PWPB95) with customized dispersion corrections (–D3 and –NL). All-in-all, it is shown that these methods behave very accurately producing errors in the 1–2 kJ/mol range with respect to the experimental value taken into account the experimental uncertainty. These methods are thus confirmed as excellent tools for studying all kinds of interactions in chemical systems.Financial support by the “Ministerio de Economía y Competitividad” of Spain and the “European Regional Development Fund” through projects CTQ2011-27253, CTQ2012-31914, and Consolider-Ingenio CSD2007-00010 in Molecular Nanoscience, and by the Generalitat Valenciana (ISIC 2012/008 and PROMETEO/2012/053) is acknowledged. The work in Mons is supported by the Belgian National Fund for Scientific Research (FNRS). Y.O. is a FNRS Post-doctoral Research Fellow. J.C.S.G. is a FNRS Visiting Professor