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Transcorrelated theory for transition-metal atoms

Kristoffer Simula1, Maria-Andreea Filip2, and Ali Alavi1,2

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Phys. Rev. A 112, 032805 – Published 11 September, 2025

DOI: https://doi.org/10.1103/2ttg-789l

Abstract

We benchmark ionization and excitation energies of transition-metal atoms Sc–Zn with a transcorrelated Hamiltonian combined with pseudopotentials. The similarity transformed Hamiltonian provides compact transcorrelation (TC) wave functions in affordable aug-cc-pVTZ and aug-cc-pVQZ Gaussian bases and eliminates the need for complete basis set extrapolations. The use of Douglas-Kroll-Hess theory is omitted because scalar relativistic effects are included in the pseudopotentials. Treating the full semicore (3s3p) valence and freezing only 1s–2p shells, we reach chemical accuracy for all atoms and properties with coupled cluster and full configuration interaction quantum Monte Carlo. Consistent total energies across disparate orbital sets and correlation solvers highlight the robustness of the TC workflow. Our study pushes benchmark-quality quantum chemistry into the 3d block without large-scale basis sets and opens a practical route for transcorrelation to strongly correlated molecules and materials hosting heavier transition metals.

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Phys. Rev. A 112, 032805– Published 11 September, 2025
  • Received 12 June 2025
  • Accepted 8 August 2025
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Open access publication funded by Max Planck Society.

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