Combining Accuracy and Efficiency: An Incremental Focal-Point Method Based on Pair Natural Orbitals

• Published in: Journal of chemical theory and computation Vol. 13; no. 12; pp. 6023 - 6042
• Main Authors: Fiedler, Benjamin, Schmitz, Gunnar, Hättig, Christof, Friedrich, Joachim
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.12.2017
• Subjects: Accuracy; Binding energy; Efficiency; Mathematical analysis; Molecular chains; Molecular clusters; Orbitals; Parallel processing
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.7b00654

In this work, we present a new pair natural orbitals (PNO)-based incremental scheme to calculate CCSD­(T) and CCSD­(T0) reaction, interaction, and binding energies. We perform an extensive analysis, which shows small incremental errors similar to previous non-PNO calculations. Furthermore, slight PNO errors are obtained by using T PNO = T TNO with appropriate values of 10–7 to 10–8 for reactions and 10–8 for interaction or binding energies. The combination with the efficient MP2 focal-point approach yields chemical accuracy relative to the complete basis-set (CBS) limit. In this method, small basis sets (cc-pVDZ, def2-TZVP) for the CCSD­(T) part are sufficient in case of reactions or interactions, while some larger ones (e.g., (aug)-cc-pVTZ) are necessary for molecular clusters. For these larger basis sets, we show the very high efficiency of our scheme. We obtain not only tremendous decreases of the wall times (i.e., factors >102) due to the parallelization of the increment calculations as well as of the total times due to the application of PNOs (i.e., compared to the normal incremental scheme) but also smaller total times with respect to the standard PNO method. That way, our new method features a perfect applicability by combining an excellent accuracy with a very high efficiency as well as the accessibility to larger systems due to the separation of the full computation into several small increments.