Basis Set Dependence of Interaction Energies Computed Using Composite Post-MP2 Methods

0392240 - ÚOCHB 2014 RIV US eng J - Článek v odborném periodiku
Platts, J. A. - Hill, J. G. - Riley, K. E. - Řezáč, Jan - Hobza, Pavel
Basis Set Dependence of Interaction Energies Computed Using Composite Post-MP2 Methods.
Journal of Chemical Theory and Computation. Roč. 9, č. 1 (2013), s. 330-337. ISSN 1549-9618. E-ISSN 1549-9626
Grant CEP: GA ČR GBP208/12/G016
Institucionální podpora: RVO:61388963
Klíčová slova: plesset perturbation-theory * intermolecular interaction energies * density fitting approximations
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 5.310, rok: 2013

We report the performance of composite post-MP2 ab initio methods with small basis sets for description of noncovalent interactions, using the S66 data set as a benchmark. For three representative complexes, it is shown that explicitly correlated coupled cluster (CCSD-F12a) methods yield interaction energies ca. 0.1 kcal/mol from the complete basis set limit with aug-cc-pVDZ. Triple excitations are not explicitly correlated in this approach, but we show that scaling the perturbative triples via the (T*) approximation improves agreement with benchmark values. Across the entire S66 data set, this approach results in a root-mean-square error (RMSE) of 0.13 kcal/mol or 3%, with well-balanced description of all classes of complex. The basis set dependence of traditional CCSD(T) interaction energies is examined, and the small 6-31G*(0.25) basis set is found to give particularly accurate results (RMSE = 0.15 kcal/mol, or 4%). We also employ spin component scaling (SCS) of CCSD-F12a data, which gives slightly better accuracy than CCSD(T*)-F12a if contributions from same- and opposite-spin pairs are optimized for this data set (RMSE = 0.08 kcal/mol, or 2%). Interpolation of local MP2 and MP3 is also shown to accurately reproduce benchmark data with both aug-cc-pVDZ (RMSE = 0.18 kcal/mol or 5%) and 6-31G*(0.25) (RMSE = 0.13 kcal/mol or 4%).
Trvalý link: http://hdl.handle.net/11104/0221160