Physics of chemical processes

We report the synthesis and characterization of pure CuO and CuO–ZnO nanostructured composite thin films sprayed on particle-free glass substrates using chemical spray pyrolysis method. The films were systematically analyzed through microstructural, morphological, chemical, and gas-sensing studies. X-ray diffraction (XRD) studies confirmed the polycrystalline nature of the films, with a predominant monoclinic phase along the (002) direction. Key structural parameters, such as crystallite size, dislocation density, strain, and the number of crystallites per unit area, were reported from XRD analysis. Field emission scanning electron microscopy revealed a bundled-like morphology witha uniform particle distribution, enhancing the surface area for effective gas interaction. X-ray photoelectron spectroscopy results indicated that Cu and Zn ions existed predominantly in the 2+ oxidation state, contributing to the films' reactivity. Significantly, the gas sensing studies were investigated with static liquid distribution method, highlighting the remarkable performance of the 30 wt.% CuO–ZnO composite thin film. This composite exhibited a substantial response to 5 ppm formaldehyde at ambient conditions, showing a recovery time of 22 s and a response time of 15 s. These findings underscore the potential of CuO–ZnO composites for efficient formaldehyde gas sensing applications, marking a notable advancement in the field of environmental monitoring.

In this work, molecular geometric phase effects are studied using the idea of exact factorization (EF) (Abedi et al 2010 Phys. Rev. Lett. 105 123002) and exact effective force (Li et al 2022 Phys. Rev. Lett. 128 113001). In particular, we performed dynamics simulations for a two-state vibronic coupling model, and interpreted the results in three different perspectives: the Born–Huang expansion, the exact time-dependent potential energy surface (TDPES) and the exact effective force. We find that (i) at particular moment, while the vanishing nuclear density that occurs periodically in space is conventionally attributed to destructive interference of the nuclear wave packet owing to the geometric phase, such phenomenon can be equally well interpreted through the energy perspective, as manifested in the exact TDPES in the EF scheme; (ii) when combined with trajectory-based classical dynamics, the exact effective force obtained through EF qualitatively reproduces the correct nuclear density, while the adiabatic force gives the wrong density, particularly in the interference region. Our results suggest that the exact effective force is a potential starting point for making approximations and improving trajectory-based computational methods towards an accurate description of geometric phase effects.

Rectification, the preferential transport of a current in one direction through a system, has garnered significant attention in molecules because of its importance for controlling thermal and electronic currents at the nanoscale. Here, we report the presence of energy storage rectification effects in a molecular chain. This phenomenon is generated by subjecting a harmonic molecular chain to an oscillating temperature gradient and showing that the energy absorption rate of the system depends on the direction of the gradient. We examine how the energy storage rectification ratios in the chain are affected by the oscillating gradient, asymmetry in the chain, and the system parameters. We find that energy storage rectification can be observed in harmonic lattice structures with time-dependent temperatures and that, correspondingly, anharmonicity is not required to generate this rectification mechanism in such systems.

Modeling the dynamics of photoinduced charge transfer (CT) in condensed phases presents challenges due to complicated many-body interactions and the quantum nature of electronic transitions. While traditional Marcus theory is a robust method for calculating CT rate constants between electronic states, it cannot account for the nonequilibrium effects arising from the initial nuclear state preparation. In this study, we employ the instantaneous Marcus theory (IMT) to simulate photoinduced CT dynamics. IMT incorporates nonequilibrium structural relaxation following a vertical photoexcitation from the equilibrated ground state, yielding a time-dependent rate coefficient. The multistate harmonic (MSH) model Hamiltonian characterizes an organic photovoltaic carotenoid-porphyrin-fullerene triad dissolved in explicit tetrahydrofuran solvent, constructed by mapping all-atom inputs from molecular dynamics simulations. Our calculations reveal that the electronic population dynamics of the MSH models obtained with IMT agree with the more accurate quantum-mechanical nonequilibrium Fermi's golden rule. This alignment suggests that IMT provides a practical approach to understanding nonadiabatic CT dynamics in condensed-phase systems.

This paper explores yttrium and copper co-doped cobalt ferrite [Co_1−xCu_xFe_1.85Y_0.15O₄] synthesized via the sol–gel auto-combustion route (0.0 ⩽ x ⩽ 0.08). Investigating the impact of co-dopants on CoFe₂O₄, the study reveals altered cation distribution affecting the structure, multiferroic, and electrical properties. X-ray diffraction studies show nanocrystalline co-doped cobalt ferrites with lattice expansion and smaller grains due to Cu–Y co-doping. Fourier transform infrared spectroscopy confirms inverse spinel family classification with tetrahedral lattice shrinkage. Field emission scanning electron microscopy indicates a grain size of approximately 0.12 μm. Ferroelectric analysis reveals a peak saturation polarization of 23.42 μC cm⁻² for 8% copper doping, attributed to increased Fe³⁺ ions at tetrahedral sites. Saturation magnetization peaks at 54.4706 emu g⁻¹ for 2% Cu²⁺ ion substitution [Co_0.98Cu_0.02Fe_1.85Y_0.15O₄] and decreases to 37.09 emu g⁻¹ for 4% Cu substitution due to irregular iron atom distribution at tetrahedral sites. Dielectric studies uncover Maxwell–Wagner polarization and high resistance in grain and grain boundaries using impedance spectroscopy. Fabricated hydroelectric cells exhibit improved ionic diffusion, suggesting their use in potential hydroelectric cell applications.

Global energy demand has been increasing for decades, which has created a necessity for large scale energy storage solutions for renewable energy sources. We studied the voltage of vanadium redox flow batteries (VRFBs) with density functional theory (DFT) and a newly developed technique using ab initio molecular dynamics (AIMD). DFT was used to create cluster models to calculate the voltage of VRFBs. However, DFT is not suited for capturing the dynamics and interactions in a liquid electrolyte, leading to the need for AIMD, which is capable of accurately modeling such things. The molarities and densities of all systems were carefully considered to match experimental conditions. With the use of AIMD, we calculated a voltage of 1.23 V, which compares well with the experimental value of 1.26 V. The techniques developed using AIMD for voltage calculations will be useful for the investigation of potential future battery technologies or as a screening process for additives to make improvements to currently available batteries.