Coupled-Cluster in Density Functional Theory Embedding Applied to Static Polarizabilities in Aqueous Environments

2025/09/26 by Anthuan Ferino-Pérez, Thomas‐C. Jagau · 1 voice
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Molecular spectroscopy and chirality #Spectroscopy and Quantum Chemical Studies

paper · doi:10.1021/acs.jctc.5c00767

openalex publication_date 2025/09/26 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/02

Abstract

We present a study of static polarizabilities of organic molecules in aqueous environments using projection-based coupled-cluster in density functional theory quantum embedding. We propose two methods for the computation of supermolecular polarizabilities: an iterative embedding approach and a finite-field approach. The performance of these methods is tested against regular coupled-cluster singles and doubles (CCSD) theory. The static polarizability tensor of the investigated organic molecules varies only slightly with the inclusion of water molecules. The iterative CCSD-in-DFT approach produces isotropic polarizabilities of CCSD quality with mean relative errors smaller than 1.0% at a reduced computational cost, while the anisotropic polarizabilities are not as well described. The choice of the exchange correlation functional for the treatment of the environment has little impact on the quality of the iterative embedding results. On the other hand, the results of the finite-field approach heavily depend on the density functional. When the best performing functionals are used, the finite-field approach yields isotropic and anisotropic polarizabilities in very good agreement with CCSD.

Citations

• High-Precision Calculations of Dispersion Coefficients, Static Dipole Polarizabilities, and Atom-Wall Interaction Constants for Alkali-Metal Atoms
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Frozen density functional approach for ab initio calculations of solvated molecules
• Note on an Approximation Treatment for Many-Electron Systems
• A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
• Effect of the damping function in dispersion corrected density functional theory
• Density-functional thermochemistry. III. The role of exact exchange
• Generalized Gradient Approximation Made Simple
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu

Discussions

• Check out this recent paper in JCTC, in which authors pioneer the use of iterative CC-in-DFT embedding in Q-Chem to study static polarizabilities for organic molecules in aqueous environments. doi.org [bsky, 1 points, 0 comments]

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