Relativistic Dirac–Coulomb–Breit Four-Component Multireference Perturbation Theory within the Small Tensor Product Distributed Active Space Framework
Year: 2026
Type: article
Abstract: We present a four-component multireference second-order perturbation theory (4C-MRPT2) within the small tensor product distributed active space (STP-DAS) framework. The formulation is compatible with the Dirac–Coulomb (DC), Dirac–Coulomb–Gaunt (DCG), and Dirac–Coulomb–Breit (DCB) Hamiltonians and inherits the memory-efficient and massively parallel STP-DAS algorithm, enabling perturbative treatments over very large external spaces. Benchmark calculations on noble-gas and group-13 atoms demonstrate that 4C-MRPT2 efficiently recovers all-electron dynamic correlation while providing new insight into relativistic correlation effects. The calculations show that the Breit contribution to the correlation energy increases rapidly with atomic number and reaches approximately 4% of the total correlation energy for Xe. The method also shows that second-order correlation energies are only weakly dependent on the choice of multiconfigurational reference orbitals and that frozen-core and frozen-virtual approximations substantially reduce computational cost with minimal loss of accuracy.
Institution: University of Washington
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7202351966