Multiscale Quasiparticle Electronic Structure and Excitonic Properties of CdSe Nanoclusters

Abstract

Quantum confinement in stoichiometric $\mathrm{Cd}_n\mathrm{Se}_n$ nanoclusters dramatically attenuates electronic screening, driving a delicate, size-dependent competition between quasiparticle self-energy corrections ($\Delta_{\mathrm{QP}}$) and exciton binding energies ($E_b$). Here, we present a $GW$/BSE study across a representative size series ($n = 3, 6, 13, 33$) and leverage it to validate a scalable atomistic tight-binding (TB) framework derived from first principles. Our results demonstrate that 1-2 eV spectral blueshifts previously reported in the literature arise from single-particle $GW$ convergence artifacts rather than deficiencies in the electron--hole kernels. We show that the near-perfect cancellation between $\Delta_{\mathrm{QP}}$ and $E_b$ breaks down as cluster volume increases, driven by the rapid onset of dielectric screening attenuating $E_b$ faster than $\Delta_{\mathrm{QP}}$ and leading to a pronounced divergence from mean-field predictions. Spatial inverse participation ratio analysis of the electronic structure reveals that optical suppression of fundamental pre-peaks stems from a severe spatial mismatch between localized valence orbitals and delocalized conduction states. Finally, we demonstrate that the confinement-induced scaling of the quasiparticle gap and the optical onset is accurately reproduced by a scissor-corrected, DFT-parameterized TB model. As such, this work provides a quantitative multiscale roadmap for embedding effective many-body effects kernels into computationally efficient models, enabling reliable optical predictions for realistic semiconducting nanostructures containing up to thousands of atoms.