Surface Chemistry of Semiconducting Quantum Dots: Theoretical Perspectives.

Colloidal quantum dots (QDs) are near-ideal nanomaterials for energy conversion and lighting technologies. However, their photophysics exhibits supreme sensitivity to surface passivation and defects, of which control is problematic. The role of passivating ligands in photodynamics remains questionable and is a focus of ongoing research. The optically forbidden nature of surface-associated states makes direct measurements on them challenging. Therefore, computational modeling is imperative for insights into surface passivation and its impact on light-driven processes in QDs. This Account discusses challenges and recent progress in understanding surface effects on the photophysics of QDs addressed via quantum-chemical calculations. We overview different methods, including the effective mass approximation (EMA), time-dependent density functional theory (TDDFT), and multiconfiguration approaches, considering their strengths and weaknesses relevant to modeling of QDs with a complicated surface. We focus on CdSe, PbSe, and Si QDs, where calculations successfully explain experimental trends sensitive to surface defects, doping, and ligands. We show that the EMA accurately describes both linear and nonlinear optical properties of large-sized CdSe QDs (>2.5 nm), while TDDFT is required for smaller QDs where surface effects dominate. Both approaches confirm efficient two-photon absorption enabling applications of QDs as nonlinear optical materials. TDDFT also describes the effects of morphology on the optical response of QDs: the photophysics of stoichiometric, magic-sized XY (X = Cd, Pb; Y = S, Se) QDs is less sensitive to their passivation compared with nonstoichiometric XY QDs. In the latter, surface-driven optically inactive midgap states can be eliminated by anionic ligands, explaining the better emission of metal-enriched QDs compared with nonmetal-enriched QDs. Ideal passivation of magic-sized QDs by amines and phosphine oxides leaves lower-energy transitions intact, while thiol derivatives add ligand-localized trap states to the band gap. Depending on its position, any loss of ligand from the QD's surface also introduces electron or hole traps, decreasing the QD's luminescence. TDDFT investigations of QD-ligand and QD-QD interactions provide an explanation of experimentally detected enhancement of blinking on-times in closely packed Si QDs and establish favorable conditions for hole transfer from the photoexcited CdSe QD to metal-organic dyes. While TDDFT well describes qualitative trends in optical response to stoichiometry and ligand modifications of QDs, it is unable to calculate highly correlated electronic states like biexcitons and magnetic-dopant-derived states. In these cases, multiconfiguration methods are applied to small nanoclusters and the results are extrapolated to larger-sized QDs, providing reasonable explanations of experimental observables. For light-driven dynamics, the electron-phonon couplings are important, and nonadiabatic dynamics (NAD) is applied. NAD based on first-principles calculations is a current grand challenge for the theory. However, it can be accomplished through sets of semiclassical approximations such as surface hopping (SH). We discuss validations of approximations used in photodynamics of ligated and doped QDs. Time-domain DFT-based SH-NAD reveals the ligand's role in ultrafast energy relaxation and the connection between the phonon bottleneck and the Zeno effect in CdSe QDs. The calculated results are helpful in controlling both dissipation and radiative processes in QDs via surface engineering and in explanations of experimental data.