Highlights • Reverse logistics of a green supply chain with environmentally-conscious customers is addressed. • Customer word-of-mouth effect is taken into account. • Two different pricing strategies and three game theoretic models have been derived and compared. • Results indicate customer environmental awareness has positive effects on revenues.

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Understanding hot carrier dynamics between plasmonic nanomaterials and its adsorbate is of great importance for plasmon‐enhanced photoelectronic processes such as photocatalysis, optical sensing and spectroscopic analysis. However, it is often challenging to identify specific dominant mechanisms for a given process because of the complex pathways and ultrafast interactive dynamics of the photoelectrons. Here, using CO2 reduction as an example, the underlying mechanisms of plasmon‐driven catalysis at the single‐molecule level using time‐dependent density functional theory calculations is clearly probed. The CO2 molecule adsorbed on two typical nanoclusters, Ag20 and Ag147, is photoreduced by optically excited plasmon, accompanied by the excitation of asymmetric stretching and bending modes of CO2. A nonlinear relationship has been identified between laser intensity and reaction rate, demonstrating a synergic interplay and transition from indirect hot‐electron transfer to direct charge transfer, enacted by strong localized surface plasmons. These findings offer new insights for CO2 photoreduction and for the design of effective pathways toward highly efficient plasmon‐mediated photocatalysis.

The past decades have witnessed the success of ground‐state density functional theory capturing static electronic properties of various materials. However, for time dependent processes especially those involving excited states, real‐time time‐dependent density functional theory (rt‐TDDFT) and advanced nonadiabatic algorithms are essential, especially for practical simulations of molecules and materials under the occurrence of ultrafast laser field. Here we summarize the recent progresses in developing rt‐TDDFT approaches within numerical atomic orbitals and planewave formalisms, as well as the efforts combining rt‐TDDFT and ring polymer molecular dynamics to take into account nuclear quantum effects in quantum electronic‐nuclear dynamic simulations. Typical applications of first‐principles dynamics of excited electronic states including high harmonic generation, charge density wave, photocatalytic water splitting, as well as quantum nuclear motions in ozone and graphene, are presented to demonstrate the features and advantages of these methods. The progresses in method developments and practical applications provide unprecedented insights into nonadiabatic dynamics of excited states in the Ehrenfest scheme and beyond, towards a comprehensive understanding of excited electronic structure, electron–phonon interactions, photoinduced charge transfer and chemical reactions, as well as quantum nuclear motions in excited states. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Density Functional Theory Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods

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Nonequilibrium electron−phonon coupling (EPC) serves as a dominant interaction in a multitude of transient processes, including photoinduced phase transitions, coherent phonon generation, and possible light-induced superconductivity.Here we use monolayer MoS 2 as a prototype to investigate the variation in electron−phonon couplings under laser excitation, on the basis of real-time time-dependent density functional theory simulations. Phonon softening, anisotropic modification of the deformation potential, and enhancement of EPC are observed, which are attributed to the reduced electronic screening and modulated potential energy surfaces by photoexcitation. Furthermore, by tracking the transient deformation potential and nonthermal electronic population, we can monitor the ultrafast time evolution of the energy exchange rate between electrons and phonons upon laser excitation. This work provides an effective strategy to investigate the nonequilibrium EPC and constructs a scaffold for understanding nonequilibrium states beyond the multitemperature models.

To elucidate the nature of light-driven photocatalytic water splitting, a polymeric semiconductorgraphitic carbon nitride (g-C3N4)has been chosen as a prototype substrate for studying atomistic water spitting processes in realistic environments. Our nonadiabatic quantum dynamics simulations based on real-time time-dependent density functional theory reveal explicitly the transport channel of photogenerated charge carriers at the g-C3N4/water interface, which shows a strong correlation to bond re-forming. A three-step photoreaction mechanism is proposed, whereas the key roles of hole-driven hydrogen transfer and interfacial water configurations were identified. Immediately following photocatalytic water splitting, atomic pathways for the two dissociated hydrogen atoms approaching each other and forming the H2 gas molecule are demonstrated, while the remanent OH radicals may form intermediate products (e.g., H2O2). These results provide critical new insights for the characterization and further development of efficient water-splitting photocatalysts from a dynamic perspective.

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