Toward Reliable Dipole Moments without Single Excitations: The Role of Orbital Rotations and Dynamical Correlation

• Published in: Journal of chemical theory and computation Vol. 20; no. 11; pp. 4689 - 4702
• Main Authors: Chakraborty, Rahul, de Moraes, Matheus Morato F., Boguslawski, Katharina, Nowak, Artur, Świerczyński, Julian, Tecmer, Paweł
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 11-06-2024
• Subjects: Accuracy; Chemical bonds; Clusters; Dipole moments; Electron density; Electronic structure; Linearization; Molecular properties; Molecular structure; Quantum Electronic Structure; Structural reliability
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.4c00471

The dipole moment is a crucial molecular property linked to a molecular system’s bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used to assess the accuracy and reliability of new electronic structure methods. This work analyses electronic dipole moments computed with the pair coupled cluster doubles (pCCD) ansätze and its linearized coupled cluster (pCCD-LCC) corrections using the canonical Hartree–Fock and pCCD-optimized (localized) orbital bases. The accuracy of pCCD-based dipole moments is assessed against experimental and CCSD­(T) reference values using relaxed and unrelaxed density matrices and different basis set sizes. Our test set comprises molecules of various bonding patterns and electronic structures, exposing pCCD-based methods to a wide range of electron correlation effects. Additionally, we investigate the performance of pCCD-in-DFT dipole moments of some model complexes. Finally, our work indicates the importance of orbital relaxation in the pCCD model and shows the limitations of the linearized couple cluster corrections in predicting electronic dipole moments of multiple-bonded systems. Most importantly, pCCD with a linearized CCD correction can reproduce the dipole moment surfaces in singly bonded molecules, which are comparable to the multireference ones.