Explicitly correlated PNO-MP2 and PNO-CCSD and its application to the S66 set and large molecular systems

Gunnar Schmitz1,a), Christof Hättig1,b), and David P. Tew 2
1 Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44801 Bochum, Germany
2 Center for Computational Chemistry, University of Bristol, Bristol BS8 1TS, UK

Phys. Chem. Chem. Phys., 2014, 16 (40), 22167 - 22178
(Received 6th August 2014; accepted 3rd September 2014)

We present our current progress on the combination of explicit electron correlation with the pair natural orbital (PNO) representation. In particular we show cubic scaling PNO-MP2-F12, PNO-CCSE(2)F12 and PNO-CCSD[F12] implementations. The PNOs are constructed using a hybrid scheme, where the PNOs are generated in a truncated doubles space, spanned by orbital specific virtuals obtained using an iterative eigenvector algorithm. We demonstrate the performance of our implementation through calculations on a series of Glycine chains. The accuracy of the local approximations is assessed using the S66 benchmark set, and we report for the first time explicitly correlated CCSD results for the whole set and improved estimates for the CCSD/CBS limits. For several dimers the PNO-CCSD[F12] calculations are more accurate than the current reference values. Additionally, we present pilot applications of our PNO-CCSD[F12] code to host-guest interactions in a cluster model for zeolite H-ZSM-5 and in a calix[4]arene water complex.

a) Electronic mail: gunnar.schmitz@rub.de
b) Electronic mail: christof.haettig@rub.de

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