Origin of Vibronic Coherences During Carrier Cooling in Colloidal Quantum Dots.

Recent two-dimensional electronic spectroscopy experiments [Tilluck et al. J. Phys. Chem. Lett. 2021, 12 (39), 9677-9683] indicate the creation of coherent vibronic wavepackets in the first femtoseconds of hot carrier cooling in hexadecylamine-passivated CdSe quantum dots. Here we present a quantum chemical study of the origin of these coherences in a CdSe nanocrystal. We find that coherent wavepacket motions along vibrational coordinates with alkylamine character promote nonradiative relaxation through conical intersections between the exciton states of the inorganic core. Electronic excitations in the core are found to pass energy to the vibrations of the ligands via two distinct mechanisms: excitation of core phonon modes that are coupled to the ligand vibrations and direct excitation of ligand vibrations by delocalization of the exciton onto the ligands, both of which naturally arise within a photochemical framework based on many-electron potential energy surfaces. If these findings are demonstrated to be general, vibronic coherences may be leveraged to control photophysical outcomes in colloidal quantum dots.

What is the Mechanism of H3+ Formation from Cyclopropane?

We examine the possibility that three hydrogen atoms in one plane of the cyclopropane dication come together in a concerted "ring-closing" mechanism to form H3+, a crucial cation in interstellar gas-phase chemistry. Ultrafast strong-field ionization followed by disruptive probing measurements indicates that the formation time of H3+ is 249 ± 16 fs. This time scale is not consistent with a concerted mechanism, but rather a process that is preceded by ring opening. Measurements on propene, an isomer of cyclopropane, reveal the H3+ formation time to be 225 ± 13 fs, a time scale similar to the H3+ formation time in cyclopropane. Ab initio molecular dynamics simulations and the fact that both dications share a common potential energy surface support the ring-opening mechanism. The reaction mechanism following double ionization of cyclopropane involves ring opening, then H-migration, and roaming of a neutral H2 molecule, which then abstracts a proton to form H3+. These results further our understanding of complex interstellar chemical reactions and gas-phase reaction dynamics relevant to electron ionization mass spectrometry.

Vibronic Excitons and Conical Intersections in Semiconductor Quantum Dots.

Surface defects and organic surface-capping ligands affect the photoluminescence properties of semiconductor quantum dots (QDs) by altering the rates of competing nonradiative relaxation processes. In this study, broadband two-dimensional electronic spectroscopy reveals that absorption of light by QDs prepares vibronic excitons, excited states derived from quantum coherent mixing of the core electronic and ligand vibrational states. Rapidly damped coherent wavepacket motions of the ligands are observed during hot-carrier cooling, with vibronic coherence transferred to the photoluminescent state. These findings suggest a many-electron, molecular theory for the electronic structure of QDs, which is supported by calculations of the structures of conical intersections between the exciton potential surfaces of a small ammonia-passivated model CdSe nanoparticle.