Mandalia R, Fauser S, Trushin E, Görling A (2025)
Publication Type: Journal article
Publication year: 2025
Book Volume: 162
Article Number: 184106
Journal Issue: 18
DOI: 10.1063/5.0267912
In the present paper, we assess the performance of methods based on the random phase approximation (RPA) and on σ-functionals for predicting static optical properties, i.e., dipole moment, polarizability, and first and second hyperpolarizability, of small- and medium-sized molecules, including chain-like systems. First, we provide accurate reference data by coupled-cluster singles, doubles, with perturbative triples calculations with sufficiently large basis sets. The RPA and σ-functional calculations are carried out post-self-consistently using input orbitals and eigenvalues from the hybrid density-functional calculation. The optimal fraction of exact non-local exchange in these calculations is found to be quite high, around 0.5-0.6 in RPA and around 0.8-1.0 in σ-functional methods. σ-functional methods, however, proved to be less sensitive than RPA methods with respect to the amount of exact non-local exchange used in the generation of their input data. σ-functional methods are shown to outperform in accuracy RPA methods and various other considered density-functional theory methods for static optical properties and, thus, are well-suited for the calculation of linear and non-linear optical properties.
APA:
Mandalia, R., Fauser, S., Trushin, E., & Görling, A. (2025). Assessment of RPA and σ-functional methods for the calculation of dipole moments and static polarizabilities and hyperpolarizabilities. Journal of Chemical Physics, 162(18). https://doi.org/10.1063/5.0267912
MLA:
Mandalia, Raviraj, et al. "Assessment of RPA and σ-functional methods for the calculation of dipole moments and static polarizabilities and hyperpolarizabilities." Journal of Chemical Physics 162.18 (2025).
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