Unveiling Hidden Shake-Up Features in the Uranyl M-Edge Spectrum.

The M-edge high energy resolution X-ray absorption near-edge structure (HR-XANES) spectra of actinyls offer valuable insights into the electronic structure and bonding properties of heavy-element complexes. To conduct a comprehensive spectral analysis, it is essential to employ computational methods that accurately account for relativistic effects and electron correlation. In this work, we utilize variational relativistic multireference configurational interaction methods to compute and analyze the X-ray M-edge absorption spectrum of uranyl.

Improving One-Electron Exact-Two-Component Relativistic Methods with the Dirac-Coulomb-Breit-Parameterized Effective Spin-Orbit Coupling.

In photochemical processes, spin-orbit coupling plays a crucial role in determining the outcome of the reaction. However, the exact treatment of the Dirac-Coulomb-Breit two-electron operator required for rigorous inclusion of spin-orbit coupling is computationally prohibitive. To address this challenge, we present a Dirac-Coulomb-Breit-parameterized screened-nuclear spin-orbit factor to approximate two-electron spin-orbit couplings in the effective one-electron spin-orbit Hamiltonian.

Scalar Breit interaction for molecular calculations.

Variational treatment of the Dirac-Coulomb-Gaunt or Dirac-Coulomb-Breit two-electron interaction at the Dirac-Hartree-Fock level is the starting point of high-accuracy four-component calculations of atomic and molecular systems. In this work, we introduce, for the first time, the scalar Hamiltonians derived from the Dirac-Coulomb-Gaunt and Dirac-Coulomb-Breit operators based on spin separation in the Pauli quaternion basis. While the widely used spin-free Dirac-Coulomb Hamiltonian includes only the direct Coulomb and exchange terms that resemble nonrelativistic two-electron interactions, the scalar Gaunt operator adds a scalar spin-spin term.

Efficient evaluation of the Breit operator in the Pauli spinor basis.

The frequency-independent Coulomb-Breit operator gives rise to the most accurate treatment of two-electron interaction in the non-quantum-electrodynamics regime. The Breit interaction in the Coulomb gauge consists of magnetic and gauge contributions. The high computational cost of the gauge term limits the application of the Breit interaction in relativistic molecular calculations.

Improving small molecule force fields by identifying and characterizing small molecules with inconsistent parameters.

Many molecular simulation methods use force fields to help model and simulate molecules and their behavior in various environments. Force fields are sets of functions and parameters used to calculate the potential energy of a chemical system as a function of the atomic coordinates. Despite the widespread use of force fields, their inadequacies are often thought to contribute to systematic errors in molecular simulations.