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The structural, photophysical, and photochemical properties of Ln(depma)(hmpa)2(NO3)3(Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes 1-Lnwere investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln3+ion the isostructural 1-Lncomplexes exhibit quite different behavior upon excitation at 350–400 nm. Some 1-Lncomplexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. 1-Euis not emissive at all, whereas 1-Nd, 1-Ho, and 1-Erexhibit a Ln3+based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light 1-Ln(Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas 1-Ln(Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln3+ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln3+ion regulated photophysics and photochemistry of the 1-Lncomplexes.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

The synthesis of 1-aminonorbornane (1-aminoNB), a potential aniline bioisostere, through photochemistry or photoredox catalysis signifies a remarkable breakthrough with implications in organic chemistry, pharmaceutical chemistry, and sustainable chemistry. However, an understanding of the underlying mechanisms involved in these reactions remains limited and ambiguous. Herein, we employ high-precision CASPT2//CASSCF calculations to elucidate the intricate mechanisms regulating the intramolecular photo-(3 + 2)-cycloaddition reactions for the synthesis of 1-aminoNB in the presence or absence of the Ir-complex-based photocatalyst. Our investigations delve into radical cascades, stereoselectivity, particularly single-electron-transfer (SET) events, etc. Furthermore, we innovatively introduce and compare two SET models integrating Marcus electron-transfer theory and transition-state theory. These models combined with kinetic data contribute to recognizing the critical control factors in diverse photocatalysis, thereby guiding the design and manipulation of photoredox catalysis as well as the improvement and modification of photocatalysts.

Polarons play a major role in determining the chemical properties of transition-metal oxides. Recent experiments show that adsorbates can attract inner polarons to surface sites. These findings require an atomistic understanding of the adsorbate influence on polaron dynamics and lifetime. We consider reduced rutile TiO2(110) with an oxygen vacancy as a prototypical surface and a CO molecule as a classic probe and perform ab initioadiabatic molecular dynamics, time-domain density functional theory, and nonadiabatic molecular dynamics simulations. The simulations show that subsurface polarons have little influence on CO adsorption and CO can desorb easily. On the contrary, surface polarons strongly enhance CO adsorption. At the same time, the adsorbed CO attracts polarons to the surface, allowing them to participate in catalytic processes with CO. The CO interaction with polarons changes their orbital origin, suppresses polaron hopping, and stabilizes them at surface sites. Partial delocalization of polarons onto CO decouples them from free holes, decreasing the nonadiabatic coupling and shortening the quantum coherence time, thereby reducing charge recombination. The calculations demonstrate that CO prefers to adsorb at the next-nearest-neighbor five-coordinated Ti3+surface electron polaron sites. The reported results provide a fundamental understanding of the influence of electron polarons on the initial stage of reactant adsorption and the effect of the adsorbate–polaron interaction on the polaron dynamics and lifetime. The study demonstrates how charge and polaron properties can be controlled by adsorbed species, allowing one to design high-performance transition-metal oxide catalysts.

Anatase TiO2is an intensely investigated photocatalytic material due to its abundance and chemical stability. However, it suffers from weak light harvesting and low photocatalytic efficiency. Experiments show that light absorption and photocatalytic properties can be enhanced simultaneously by TiO2doping with well-dispersed Cu atoms, forming a single-atom catalyst (Cu/TiO2) that can be used for solar water splitting and other applications. By performing ab initio nonadiabatic molecular dynamics simulations, we demonstrate that Cu/TiO2is inactive before light irradiation due to rapid electron–hole recombination via both shallow and deep traps. Surprisingly, the shallow trap is more detrimental to the Cu/TiO2performance than the deep trap because it couples better to free carriers. After light irradiation, leading to electron transfer and Cu/TiO2protonation, the shallow trap is eliminated, and a local distortion around the Cu atom stabilizes the deep trap state on the Cu d-orbital, decoupling it from free charges and giving rise to high photocatalytic hydrogen generation activity. We further demonstrate that the photocatalytic performance of Cu/TiO2can be enhanced by spin selection, achievable experimentally via optical intersite spin transfer or chiral semiconductor coating. Both H adsorption and spin selection enhance charge carrier lifetimes by an order of magnitude. The spin selection mechanism does not require formation of the H species, which necessitates concurrent sources of electrons and protons and which is intrinsically unstable because water splitting involves frequent proton shuffling. Our results rationalize the experimental observations at the atomistic level, provide mechanistic insights into operation of single atom photocatalysis, and demonstrate that spin selection can be used to develop advanced and efficient systems for solar energy conversion.

Understanding of photoinduced interfacial carrier dynamics in organic-transition metal dichalcogenides heterostructures is very important for the enhancement of their potential photoelectronic conversion efficiencies. In this work we have used density functional theory (DFT) calculations and DFT-based fewest-switches surface-hopping dynamics simulations to explore the photoinduced hole transfer and subsequent nonadiabatic electron–hole recombination dynamics taking place at the interface of pentacene and MoS2in pentacene@MoS2. Upon photoexcitation the electronic transition mainly occurs on the MoS2monolayer, which corresponds to moving an electron to the MoS2conduction band. As a result, a hole is left in the valence band. This hole state is energetically lower than certain occupied states of the pentacene molecule; thus, the interfacial hole transfer from MoS2to pentacene is favorable in energy. In terms of nonadiabatic dynamics simulations, the hole transfer time to the HOMO–1 state of the pentacene is estimated to be about 600 fs; however, the following hole relaxation process from HOMO–1 to HOMO takes much longer time of ca. 15 ps due to the large energy gap between HOMO–1 and HOMO. Moreover, our results also show that the subsequent radiationless recombination process between the hole transferred to the pentacene molecule and the remaining electron on the MoS2CBM needs about 10.2 ns. The computational results shed important mechanistic insights on the interfacial carrier dynamics of mixed-dimensional pentacene@MoS2. These insights could help to design excellent interfaces for organic-TMDs heterostructures.

Machine learning is capable of effectively predicting the potential energies of molecules in the presence of high-quality data sets. Its application in the construction of ground- and excited-state potential energy surfaces is attractive to accelerate nonadiabatic molecular dynamics simulations of photochemical reactions. Because of the huge computational cost of excited-state electronic structure calculations, the construction of a high-quality data set becomes a bottleneck. In the present work, we first built two data sets. One was obtained from surface hopping dynamics simulations at the semiempirical OM2/MRCI level. Another was extracted from the dynamics trajectories at the CASSCF level, which was reported previously. The ground- and excited-state potential energy surfaces of ethylene-bridged azobenzene at the CASSCF computational level were constructed based on the former low-level data set. Although non-neural network machine learning methods can achieve good or modest performance during the training process, only neural network models provide reliable predictions on the latter external test data set. The BPNN and SchNet combined with the Δ-ML scheme and the force term in the loss functions are recommended for dynamics simulations. Then, we performed excited-state dynamics simulations of the photoisomerization of ethylene-bridged azobenzene on machine learning potential energy surfaces. Compared with the lifetimes of the first excited state (S1) estimated at different computational levels, our results on the Eisomer are in good agreement with the high-level estimation. However, the overestimation of the Zisomer is unimproved. It suggests that smaller errors during the training process do not necessarily translate to more accurate predictions on high-level potential energies or better performance on nonadiabatic dynamics simulations, at least in the present case.