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We present a nonadiabatic molecular dynamics study of the ultrafast processes occurring in uracil upon UV light absorption, leading to electronic excitation and subsequent nonradiative decay. Previous studies have indicated that the mechanistic details of this process are drastically di!erent depending on whether the process takes place in the gas phase, acetonitrile, or water. However, such results have been produced using quantum chemical methods that did not incorporate both static and dynamic electron correlation. In order to assess the previously proposed mechanisms, we simulate the photodynamics of uracil in the three environments mentioned above using quantum-classical trajectories and, for solvated uracil, hybrid quantum mechanics/ molecular mechanics (QM/MM) models driven by the rotated multistate complete active space second-order perturbation (RMS-CASPT2) method. To do so, we exploit the gradient recently made available in OpenMolcas and compare the results to those obtained using the complete active space self-consistent field (CASSCF) method only accounting for static electron correlation. We show that RMS-CASPT2 produces, in general, a mechanistic picture di!erent from the one obtained at the CASSCF level but confirms the hypothesis advanced on the basis of previous ROKS and TDDFT studies thus highlighting the importance of incorporating dynamic electron correlation in the investigation of ultrafast electronic deactivation processes.more » « less
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With the aim to construct a new type of photoswitchable photochromic material modulated by specific radiation in the microwave region, the spin dynamics of radical pairs (RPs) from ion-pair complexes between viologen and tetraarylborate compounds have been investigated in the presence of microwave (μw) radiation, using steady-state electron paramagnetic resonance (SSEPR) to follow the radical pair (RP) dynamics. This strategy is realized by excitation of the charge transfer (CT) absorption band of the ion-pair complex in the solid phase (powders and dispersed in polymer matrices) at 410 nm, which leads to electron transfer from borate to viologen, producing RPs. In the singlet excited state or Partially Separated Charge (PSC) state, an electron transfer process occurs between the ions, and the subsequent (purple) viologen radical is observed as a Fully Charge Separated (FCS) state. In solid state SSEPR experiments, μw radiation deactivates the FSC state by inducing back electron transfer, which subsequently increases the population of a Partially Separated Charge (PSC) state, recovering the initial color of the ion-pair complex. State-of-the-art photophysical and photochemical studies show that deactivation of the FSC state can take place using μw radiation on the RPs in a switchable, reversible fashion. The results have potential impact for a number of applications including photo-writing and photo-erasing processes and spintronics. Examples of laser writing using a polymer matrix to lock the relative positions of the radicals, and then erasing the color using microwaves, are presented and discussed.more » « less
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null (Ed.)Colloidal semiconductor nanocrystals (NCs) represent a promising class of nanomaterials for lasing applications. Currently, one of the key challenges facing the development of high-performance NC optical gain media lies in enhancing the lifetime of biexciton populations. This usually requires the employment of charge-delocalizing particle architectures, such as core/shell NCs, nanorods, and nanoplatelets. Here, we report on a two-dimensional nanoshell quantum dot (QD) morphology that enables a strong delocalization of photoinduced charges, leading to enhanced biexciton lifetimes and low lasing thresholds. A unique combination of a large exciton volume and a smoothed potential gradient across interfaces of the reported CdS bulk /CdSe/CdS shell (core/shell/shell) nanoshell QDs results in strong suppression of Auger processes, which was manifested in this work though the observation of stable amplified stimulated emission (ASE) at low pump fluences. An extensive charge delocalization in nanoshell QDs was confirmed by transient absorption measurements, showing that the presence of a bulk-size core in CdS bulk /CdSe/CdS shell QDs reduces exciton–exciton interactions. Overall, present findings demonstrate unique advantages of the nanoshell QD architecture as a promising optical gain medium in solid-state lighting and lasing applications.more » « less