<div>Photoconductive Semiconductor Switches (PCSS) are metal-semiconductor-metal devices used to switch an electrical signal through photoconduction. Rapidly switched PCSS under high bias voltages have shown remarkable potential for high power electronic and electromagnetic wave generation, but are dependent on precise optoelectronic material parameters such as defect ionization energy and optical absorption. These properties can be measured but are difficult to attribute definitively to specific defects and materials without the aid of high-accuracy, predictive modeling and simulation. This work combines well-established methods for first principles electronic structure calculations such as Density Functional Theory (DFT) with novel modern approaches such as Local Moment Counter Charge (LMCC) boundary conditions to adequately describe charge states and Maximally Localized Wannier Functions (MLWF) to render the summation of optical excitation paths as computationally tractable. This approach is demonstrated to overcome previous barriers to obtaining reliable qualitative or quantitative results, such as DFT band gap narrowing and the prohibitive computational cost of coupled electron-phonon processes. This work contributes electronic structure calculations of 4H-SiC doped with first-row transition metals (V through Ni) that are consistent with prior published work where applicable and add new possibilities for prospective semi-insulating metal-semiconductor systems where investigating new dopant possibilities. The results indicate a spectrum of highly localized, mid-gap, spin-dependent defect energy levels which suggest a wider range of potential amphoteric dopants suitable for producing semi-insulating material. Additionally, this work contributes MLWF-based calculations of phonon-resolved optical properties in 3C and 4H-SiC, indirect gap semiconductors, which accurately produce the expected onset of optical absorption informed by experiment. These results were further expanded upon with small V-doped cells of 4H-SiC, which while not fully converged in terms of cell size still provided a qualitative point of comparison to the ground state results for determining the true optical excitation energy required for substantial photoconductivity. The subsequent speculative analysis suggests the importance of anisotropic absorption and alternative metal defects for optimizing high current optoelectronic devices such as PCSS.</div>