A First-Principles Benchmark of TD-DFT Functionals for the Photoabsorption of Camphorquinone: Validating a Quantum-Chemical Protocol for Dental Photoinitiator Design

This dataset supports the study “A First-Principles Benchmark of TD-DFT Functionals for the Photoabsorption of Camphorquinone: Validating a Quantum-Chemical Protocol for Dental Photoinitiator Design.” The work presents a systematic first-principles evaluation of commonly used time-dependent density functional theory (TD-DFT) functionals for modeling the primary photoabsorption of camphorquinone, a clinically established dental photoinitiator. The dataset includes all computational inputs and outputs required to reproduce the reported results, including optimized ground-state geometries, TD-DFT excitation calculations, and associated analysis files. Ground-state optimization was performed using density functional theory with the B3LYP functional and a 6-31G(d) basis set under an implicit polarizable continuum model representing a resin-relevant dielectric environment (ε = 4.0). Vertical electronic excitations were subsequently computed using TD-DFT with B3LYP, PBE0, CAM-B3LYP, and ωB97XD functionals under consistent methodological conditions. Benchmarking focuses on the lowest optically allowed singlet excitation of camphorquinone, with computed absorption maxima compared directly against the experimentally established peak near 468 nm. Natural Transition Orbital (NTO) data are provided to support assignment of the excitation character as a localized carbonyl-centered n(O) → π*(C=O) transition. The dataset is intended to facilitate transparency, reproducibility, and critical evaluation of functional performance for this system. All files are provided to enable independent verification, methodological comparison, and reuse in future mechanistic studies or in silico screening of related carbonyl-based photoinitiators. The scope of the data is explicitly limited to vertical excitation benchmarking under an implicit solvent model and does not imply general functional transferability beyond the studied system.