%0 Journal Article %1 publ9349428 %A Ma, Qianli %A Schwilk, Max %A Köppl, Christoph %A Werner, Hans Joachim %D 2017 %J J. Chem. Theory Comput. %K chemie imported werner from:alexanderdenzel theoretische stuttgart theochem %N 10 %P 4871–4896 %R 10.1021/acs.jctc.7b00799 %T Scalable Electron Correlation Methods. 4. Parallel Explicitly Correlated Local Coupled Cluster with Pair Natural Orbitals (PNO-LCCSD-F12) %U http://dx.doi.org/10.1021/acs.jctc.7b00799 %V 13 %X We present an efficient explicitly correlated pair natural orbital local coupled cluster (PNO-LCCSD-F12) method. The method is an extension of our previously reported PNO-LCCSD approach (Schwilk et al., J. Chem. Theory Comput. 2017, 13, 3650−3675). Near linear scaling with the molecular size is achieved by using pair, domain, and projection approximations, local density fitting and local resolution of the identity, and by exploiting the sparsity of the local molecular orbitals as well as of the projected atomic orbitals. The effect of the various domain approximations is tested for a wide range of chemical reactions and intermolecular interactions. In accordance with previous findings, it is demonstrated that the F12 terms significantly reduce the domain errors. The convergence of the reaction and interaction energies with respect to the parameters that determine the domain sizes and pair approximations is extensively tested. The results obtained with our default thresholds agree within a few tenths of a kcal mol-1 with the ones computed with very tight options. For cases where canonical calculations are still feasible, the relative energies of local and canonical calculations agree within similar error bounds. The PNO-LCCSD-F12 method needs only 25-40% more computer time than a corresponding PNO-LCCSD calculation while greatly improving the accuracy. Our program is well parallelized and capable of computing accurate correlation energies for molecules with more than 150 atoms using augmented triple-ζ basis sets and more than 5000 basis functions. Using several nodes of a small computer cluster, such calculations can be carried out within a few hours.

@article{publ9349428, abstract = {We present an efficient explicitly correlated pair natural orbital local coupled cluster (PNO-LCCSD-F12) method. The method is an extension of our previously reported PNO-LCCSD approach (Schwilk et al., J. Chem. Theory Comput. 2017, 13, 3650−3675). Near linear scaling with the molecular size is achieved by using pair, domain, and projection approximations, local density fitting and local resolution of the identity, and by exploiting the sparsity of the local molecular orbitals as well as of the projected atomic orbitals. The effect of the various domain approximations is tested for a wide range of chemical reactions and intermolecular interactions. In accordance with previous findings, it is demonstrated that the F12 terms significantly reduce the domain errors. The convergence of the reaction and interaction energies with respect to the parameters that determine the domain sizes and pair approximations is extensively tested. The results obtained with our default thresholds agree within a few tenths of a kcal mol-1 with the ones computed with very tight options. For cases where canonical calculations are still feasible, the relative energies of local and canonical calculations agree within similar error bounds. The PNO-LCCSD-F12 method needs only 25-40% more computer time than a corresponding PNO-LCCSD calculation while greatly improving the accuracy. Our program is well parallelized and capable of computing accurate correlation energies for molecules with more than 150 atoms using augmented triple-ζ basis sets and more than 5000 basis functions. Using several nodes of a small computer cluster, such calculations can be carried out within a few hours.}, added-at = {2019-03-01T15:49:38.000+0100}, author = {Ma, Qianli and Schwilk, Max and K{\"{o}}ppl, Christoph and Werner, Hans Joachim}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/22acecf2de90a9e7a2805d512ebc0e52c/theochem}, doi = {10.1021/acs.jctc.7b00799}, interhash = {8384b384b2964d5a5cf407912574cc65}, intrahash = {2acecf2de90a9e7a2805d512ebc0e52c}, issn = {15499626}, journal = {J. Chem. Theory Comput.}, keywords = {chemie imported werner from:alexanderdenzel theoretische stuttgart theochem}, number = 10, pages = {4871–4896}, timestamp = {2019-03-01T14:49:38.000+0100}, title = {{Scalable Electron Correlation Methods. 4. Parallel Explicitly Correlated Local Coupled Cluster with Pair Natural Orbitals (PNO-LCCSD-F12)}}, url = {http://dx.doi.org/10.1021/acs.jctc.7b00799}, volume = 13, year = 2017 }