Computational Investigation of the Metal and Ligand Substitution Effects on the Structure and Electronic States of the Phosphoranimide Tetramer Complexes of Cu(I), Ni(I), Co(I), and Fe(I).

The structurally unique saddle-shaped paramagnetic tetrametallic clusters of Co(I) and Ni(I) with phosphoranimide ligands have been synthesized and proposed as catalyst precursors. The analogous Cu(I) nanocluster is planar and diamagnetic. These notable variations in geometry and ground electronic states indicate that the effect of metal and ligand substituents on the structure and electronic properties of these complexes requires investigation. We present a computational study of a series of these novel homoleptic complexes containing Co(I), Ni(I), and Cu(I) as well as Fe(I) coordinated to phosphoranimides with electron-donating and withdrawing substituents, conducted at the relativistic density functional theory level using ZORA-PBE/TZP. The optimized structures of the saddle-shaped Co(I) and Ni(I) and planar Cu(I) tetramers with linear N-M-N coordination are validated with respect to X-ray diffraction determinations. The ground-state analysis indicates that Cu(I) complexes are diamagnetic, whereas Ni(I) and Co(I) complexes are in high-spin states, in agreement with magnetic susceptibility measurements. The computational results show that Fe(I) complexes are saddle shaped and high spin. The Co(I) complex is stabilized by a metal macrocycle distortion from square to diamond, as elucidated from its Walsh diagram. The effects of metals and ligand substituents on the ground electronic state, metal center coordination environment, and energy of the complexes are investigated. The bulky tertiary butyl substituent causes the largest saddle-shape distortion of the tetramer marcocycle, which partially offsets its electron-donating effect. Macrocycle distortions with N-M-N site angles ranging from obtuse to alternating obtuse reflex are correlated with the increasing number of unpaired electrons. The phenyl-substituted complexes are expected to have the highest reactivity toward electrophiles. Understanding the interplay between structural and electronic parameters is intended to guide the development of synthetic cooperative systems for multielectron redox reactions, models of biological systems, and molecular magnets.

Feasibility of streamline upwind Petrov-Galerkin angular stabilization of the linear Boltzmann transport equation with magnetic fields.

To accurately model dose in a magnetic field, the Lorentz force must be included in the traditional linear Boltzmann transport equation (LBTE). Both angular and spatial stabilization are required to deterministically solve this equation. In this work, a streamline upwind Petrov-Galerkin (SUPG) method is applied to achieve angular stabilization of the LBTE with magnetic fields. The spectral radius of the angular SUPG method is evaluated using a Fourier analysis method to characterize the convergence properties. Simulations are then performed on homogeneous phantoms and two heterogeneous slab geometry phantoms containing water, bone, lung/air and water for 0.5 T parallel and 1.5 T perpendicular magnetic field configurations. Fourier analysis determined that the spectral radius of the SUPG scheme is unaffected by magnetic field strength and the SUPG free parameter, indicating that the Gauss-Seidel source iteration method is unconditionally stable and the convergence rate is not degraded with increasing magnetic field strength. 100% of simulation points passed a 3D gamma analysis at a 2%/2 mm (3%/3 mm) gamma criterion for both magnetic field configurations in the homogeneous phantom study, with the exception of the 1.5 T perpendicular magnetic field in the pure lung phantom where a 77.4% (87.0%) pass rate was achieved. Simulations in the lung slab geometry phantom resulted in 100% of points passing a 2%/2 mm gamma analysis in a 0.5 T parallel magnetic field, and 97.7% (98.8%) of points passing a 2%/2 mm (3%/3 mm) gamma criterion in a 1.5 T perpendicular magnetic field. For the air slab geometry phantom, 72.1% (79.2%) of points passed a 2%/2 mm gamma criterion in a 0.5 T parallel magnetic field and 90.3% (92.8%) passed the same gamma criterion in a 1.5 T perpendicular magnetic field. While the novel SUPG angular stabilization method shows feasibility in some cases, it was found that the accuracy of this method was degraded for very low density media such as air.

Corrigendum to "Stability analysis of a deterministic dose calculation for MRI-guided radiotherapy".

Modern effort in radiotherapy to address the challenges of tumor localization and motion has led to the development of MRI guided radiotherapy technologies. Accurate dose calculations must properly account for the effects of the MRI magnetic fields. Previous work has investigated the accuracy of a deterministic linear Boltzmann transport equation (LBTE) solver that includes magnetic field, but not the stability of the iterative solution method. In this work, we perform a stability analysis of this deterministic algorithm including an investigation of the convergence rate dependencies on the magnetic field, material density, energy, and anisotropy expansion. The iterative convergence rate of the continuous and discretized LBTE including magnetic fields is determined by analyzing the spectral radius using Fourier analysis for the stationary source iteration (SI) scheme. The spectral radius is calculated when the magnetic field is included (1) as a part of the iteration source, and (2) inside the streaming-collision operator. The non-stationary Krylov subspace solver GMRES is also investigated as a potential method to accelerate the iterative convergence, and an angular parallel computing methodology is investigated as a method to enhance the efficiency of the calculation. SI is found to be unstable when the magnetic field is part of the iteration source, but unconditionally stable when the magnetic field is included in the streaming-collision operator. The discretized LBTE with magnetic fields using a space-angle upwind stabilized discontinuous finite element method (DFEM) was also found to be unconditionally stable, but the spectral radius rapidly reaches unity for very low density media and increasing magnetic field strengths indicating arbitrarily slow convergence rates. However, GMRES is shown to significantly accelerate the DFEM convergence rate showing only a weak dependence on the magnetic field. In addition, the use of an angular parallel computing strategy is shown to potentially increase the efficiency of the dose calculation.