Insights into the Ultrafast Dynamics of CH2 OO and CH3 CHOO Following Excitation to the Bright 1 ππ* State: The Role of Singlet and Triplet States.

Criegee intermediates make up a class of molecules that are of significant atmospheric importance. Understanding their electronically excited states guides experimental detection and provides insight into whether solar photolysis plays a role in their removal from the troposphere. The latter is particularly important for large and functionalized Criegee intermediates. In this study, the excited state chemistry of two small Criegee intermediates, formaldehyde oxide (CH2 OO) and acetaldehyde oxide (CH3 CHOO), was modeled to compare their specific dynamics and mechanisms following excitation to the bright ππ* state and to assess the involvement of triplet states to the excited state decay process. Following excitation to the bright ππ* state, the photoexcited population exclusively evolves to form oxygen plus aldehyde products without the involvement of triplet states. This occurs despite the presence of a more thermodynamically stable triplet path and several singlet/triplet energy crossings at the Franck-Condon geometry and contrasts with the photodynamics of related systems such as acetaldehyde and acetone. This work sets the foundations to study Criegee intermediates with greater molecular complexity, wherein a bathochromic shift in the electron absorption profiles may ensure greater removal via solar photolysis.

Signature of van der Waals interactions in the cumulant density matrix.

Here we propose and implement a universal signature of the van der Waals interactions based on the cumulant part of the two-electron reduced density matrix (2-RDM). Due to the connected property of the cumulant, we can use it to detect the van der Waals interactions between two molecular moieties. In particular, we use the squared Frobenius norm of the cumulant of the 2-RDM, which has been previously shown to provide a size-extensive measure of the electron correlation. As two moieties are separated to infinity, the cumulant Frobenius norm exhibits an r-6 decay to its asymptotic limit, providing a density-based measure of the van der Waals interaction. We study this signature of van der Waals forces in a collection of small molecules of varying geometries. These computations agree with experimental trends of known literature values.

Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes.

Polyelectrolyte complexation has been conventionally focused on the thermodynamic states, where assemblies have equilibrated in solutions. Far less attention has been given to complex systems that are kinetically trapped at non-equilibrium states. A combination of time-resolved dynamic light scattering, small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (Cryo-TEM) was employed here to investigate the internal structures and morphological evolution of non-equilibrium aggregates forming from a pair of two strong block polyelectrolytes over wide time and length scales. The role of formation pathways of electrostatically driven aggregates was assessed using two processing protocols: direct dissolution and salt annealing. The former led to thermodynamically stable products, while the latter resulted in kinetically trapped transient structures. After adding salt, the metastable structures gradually transformed into stable products. Cryo-TEM images showed the interconnected irregular morphologies of the aggregates, and SAXS data revealed the presence of fuzzy globular complexes with R g ∼ 10 nm within them. A two-step process in the time-dependent structural transformation was found and characterized by a fast breakdown of interconnected transient aggregates followed by a slow redistribution of the incipient individual electrostatic assemblies. Furthermore, the prolonged aggregate disintegration process fitting to a stretched exponential function unveiled the broad relaxation distribution and significant structural heterogeneity in these polyelectrolyte complex nanoaggregates. This work brings new insight into the comprehension of non-equilibrium phenomena in self-assembled electrostatic assemblies and represents a first step toward constructing far-from-equilibrium polyelectrolyte complexes de novo for future applications.