Title: Ligand Induced Size-Dependent Circular Dichroism in Quantum Dots

Abstract: Recent experiments have probed the chiral properties of semiconductor nanocrystal (NC) quantum dots (QDs), but understanding the circular dichroism lineshape, excitonic features, and ligand induction mechanism remains a challenge. We propose an atomistic pseudopotential method to model chiral ligand passivated QDs, computing circular dichroism (CD) spectra for CdSe QDs (2.6 - 3.8 nm). We find strong agreement between calculated and measured spectra, predicting consistent bisignate lineshapes with decreasing CD magnitude as size increases. Our analysis reveals the origin of bisignate lineshapes, arising from nondegenerate excitons with opposing angular momenta. We also explore the impact of chiral ligand orientation on QD surfaces, observing changes in optical activity magnitude and sign. This orientation sensitivity offers means to distinguish ordered from disordered ligand configurations, facilitating the study of order-disorder transitions at ligand-QD interfaces.