Comprehensive Benchmark Results for the Domain Based Local Pair Natural Orbital Coupled Cluster Method (DLPNO-CCSD(T)) for Closed- and Open-Shell Systems

Abstract

In this study we examine the accuracy of domain-based local pair natural orbital coupled cluster theory with single, double, and perturbative triple excitations (DLPNO-CCSD­(T)) on a large benchmark data set. To this end, we use the recently published GMTKN55 superset of molecules that contains 1505 relative energies and 2462 single-point calculations. To our knowledge this is the most comprehensive benchmark evaluation of any highly correlated wave function based ab initio method to date. In the first part of the study, canonical CCSD­(T) reference calculations were carried out on the entire test set in order to guarantee that the reference data are of uniform quality. Second, DLPNO-CCSD­(T) calculations were carried out under identical conditions. The main finding is that with the exception of two data sets, all data sets have a MAD of 0.4 kcal/mol or less and the majority of sets have a MAD of less than 0.2 kcal/mol. For open shells, the accuracy of the DLPNO calculations was significantly improved through an iterative version of the triples correction.

Assessing Conformer Energies using Electronic Structure and Machine Learning Methods

“…(Dunning 1989, Kendall 1992 This approach has been found to be a highly accurate method for calculating thermochemical properties and with significantly lower computational cost for medium to large organic molecules, compared to canonical CCSD(T) methods. 45,65,66 Since some molecules in the original test set included iodine and some DLPNO-CCSD(T) By considering a large number of diverse organic molecules with many poses per molecule, we seek to sample a wide variety of conformer energy preferences (e.g., intramolecular hydrogen and halogen bonding, -stacking, electrostatic interactions, etc.). While using optimized low-energy conformers may under-estimate the accuracy of methods for high-energy struc-tures, 7 we believe the current work is a challenging but useful comparison.…”

Local energy decomposition of coupled‐cluster interaction energies: Interpretation, benchmarks, and comparison with symmetry‐adapted perturbation theory

“…[11][12][13] In particular, the domain-based local pair natural orbital variant of the CCSD(T) method [DLPNO-CCSD(T) [13][14][15][16][17][18][19][20][21][22] ] has been shown to provide extremely accurate interaction energies, with errors that are typically below 0.2 kcal mol −1 with respect to its canonical counterpart. [22][23][24][25][26] Recently, an EDA scheme called local energy decomposition (LED) was introduced. [27] This method decomposes the accurate DLPNO-CCSD (T) interaction energy into repulsive electronic preparation, electrostatics, exchange, dispersion, and nondispersive correlation, and it is available for closed-and open-shell systems.…”

Assessing Conformer Energies using Electronic Structure and Machine Learning Methods

“…(Dunning 1989, Kendall 1992 This approach has been found to be a highly accurate method for calculating thermochemical properties and with a significantly lower computational cost for medium to large organic molecules, compared to canonical CCSD(T) methods. [66], [67], [45] Using only the set of molecules in which all standard (i.e., not machine-learning based) methods completed leaves 6511 entries. Of those, 9 molecules (out of 690) had 2 or fewer poses and were also removed, leaving 681 unique molecules and˜6500 entries for comparison.…”