While the ab initio molecular dynamics (AIMD) approach to gas− surface interaction has been instrumental in exploring important issues such as energy transfer and reactivity, it is only amenable to short-time events and a limited number of trajectories because of the on-the-fly nature of the density functional theory (DFT) calculations. Here, we report a high-dimensional global reactive potential energy surface (PES) constructed with high fidelity from judiciously placed DFT points, using a machine learning method; and it is ordersof-magnitude more efficient than AIMD in dynamical calculations and can be employed in various simulations without performing additional electronic structure calculations. Importantly, the surface atoms are included in such a PES, which provides a unique platform for studying energy transfer and scattering/ reaction of the impinging molecule on the solid surface on an equal footing.

Localized surface plasmon resonances (LSPRs) have attracted much recent attention for their potential in promoting chemical reactions with light. However, the mechanism of LSPR-induced chemical reactions is still not clear, even for H2 dissociation on metal nanoparticles. In this work, we investigate the mechanism for photoinduced H2 dissociation using a simple H2@Au6 model. Our time-dependent density functional theory calculations indicate that the initial excitation is largely restricted to the metal cluster, involving intraband excitation that produces hot electrons (HEs). However, diabatization via overlapping orbitals reveals two types of nested electronic states, one involving excitations of the metallic electrons, namely, the HE states, and the other concerned with charge transfer (CT) to the adsorbate antibonding σ* orbital. Dissociation of H2 thus takes place by transitions from the former to the latter. Quantum dynamics simulations on the diabatic CT states suggest rapid dissociation of H2, while no such dissociation occurs on diabatic HE states. Our research provides a clear physical picture of photoinduced H2 dissociation on Au clusters, which has important implications in plasmonic facilitated photocatalysis.

Dual-emission of the enol-forms and keto-forms of 2-(2′-hydroxyphenyl)oxazoles and their application in OLEDs are investigated.

Three-dimensional potential energy surfaces for the two lowest singlet (Ã(1)B1 and B̃(1)A2) and two lowest triplet (ã(3)B1 and b̃(3)A2) states of SO2 have been determined at the Davidson corrected internally contracted multi-reference configuration interaction level with the augmented correlation-consistent polarized triple-zeta basis set (icMRCI+Q∕AVTZ). The non-adiabatically coupled singlet states, which are responsible for the complex Clements bands of the B band, are expressed in a 2 × 2 quasi-diabatic representation. The triplet state potential energy surfaces, which are responsible for the weak A band, were constructed in the adiabatic representation. The absorption spectrum spanning both the A and B bands, which is calculated with a three-state non-adiabatic coupled Hamiltonian, is in good agreement with experiment, thus validating the potential energy surfaces and their couplings.

In this work, three azole-based ternary deep eutectic solvents (DESs) were designed for highly efficient absorption of NH3 by utilizing the weak acidity of azoles. Specifically, the DESs are composed of choline chloride (ChCl); a model azole compound such as imidazole (ImZ), triazole (TrZ), or tetrazole (TetrZ); and ethylene glycol (EG). The effects of liquid composition, pressure, and temperature on NH3 solubilities in DESs were examined systematically. It is found that ChCl + TetrZ + EG displays obvious chemical behavior for NH3 absorption owing to the relatively stronger acidity of TetrZ, and it exhibits the highest NH3 capacities among the three DESs. The NH3 capacities of ChCl + TetrZ + EG are superior to most absorbents/adsorbents previously reported, especially when compared at low pressures. Recycling experiments demonstrate that the chemical absorption of NH3 in ChCl + TetrZ + EG is reversible, with only partial loss in NH3 capacities during absorption–desorption cycles. Furthermore, theoretical calculations were performed to gain molecular insights into the absorption of NH3 in azole-based DESs.