Molecular Dipole Moments within the Incremental Scheme Using the Domain-Specific Basis-Set Approach

• Published in: Journal of chemical theory and computation Vol. 12; no. 7; pp. 3040 - 3052
• Main Authors: Fiedler, Benjamin, Coriani, Sonia, Friedrich, Joachim
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.07.2016
• Subjects: Accuracy; Automation; Computation; Computational efficiency; Dipole moment; Error correction; Parameters; Standard deviation
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.6b00076

We present the first implementation of the fully automated incremental scheme for CCSD unrelaxed dipole moments using the domain-specific basis-set approach. Truncation parameters are varied, and the accuracy of the method is statistically analyzed for a test set of 20 molecules. The local approximations introduce small errors at second order and negligible ones at third order. For a third-order incremental CCSD expansion with a CC2 error correction, a cc-pVDZ/SV domain-specific basis set (t main = 3.5 Bohr), and the truncation parameter f = 30 Bohr, we obtain a mean error of 0.00 mau (−0.20 mau) and a standard deviation of 1.95 mau (2.17 mau) for the total dipole moments (Cartesian components of the dipole vectors). By analyzing incremental CCSD energies, we demonstrate that the MP2 and CC2 error correction schemes are an exclusive correction for the domain-specific basis-set error. Our implementation of the incremental scheme provides fully automated computations of highly accurate dipole moments at reduced computational cost and is fully parallelized in terms of the calculation of the increments. Therefore, one can utilize the incremental scheme, on the same hardware, to extend the basis set in comparison to standard CCSD and thus obtain a better total accuracy.