Physical Chemistry Chemical Physics

doi: 10.1039/d2cp90122fpmid: N/A

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doi: 10.1039/d2cp90123dpmid: N/A

Meng, Qingyong; Chen, Junbo; Ma, Jianxing; Zhang, Xingyu; Chen, Jun

doi: 10.1039/d2cp01560apmid: 35766107

In this contribution, we review models for the lattice effects in quantum dynamics calculations on surface scattering, which is important to modeling heterogeneous catalysis for achieving an interpretation of experimental measurements. Unlike dynamics models for reactions in the gas phase, those for heterogeneous reactions have to include the effects of the surface. For manageable computational costs in calculations, the effects of static surface (SS) are firstly modeled as this is simply and easily implemented. Then, the SS model has to be improved to include the effects of the flexible surface, that is the lattice effects. To do this, various surface models have been designed where the coordinates of the surface atoms are introduced in the Hamiltonian operator, especially those of the top surface atom. Based on this model Hamiltonian operator, extensive multi-dimension quantum dynamics calculations can be performed to recover the lattice effects. Here, we first review an overview of the techniques in constructing the Hamiltonian operator, which is a sum of the kinetic energy operator (KEO) and potential energy surface (PES). Since the PES containing the coordinates of the surface atoms in a cell is still expensive, the SS model is often accepted. We consider a mathematical model, called the coupled harmonic oscillator (CHO) model, to introduce the concepts of adiabatic and diabatic representations for separating the molecule and surface. Under the adiabatic model, we further introduce the expansion model where the potential function is Taylor expanded around the optimized geometry of the surface. By an expansion model truncated at the first and second order, various coupling surface models between the molecule and surface are derived. Moreover, by further and deeply understanding the adiabatic representation, an effective Hamiltonian operator is obtained by optimizing the total wave function in factorized form. By this factorized form of wave function and effective Hamiltonian operator, the geometry phase of the surface wave function is theoretically found. This theoretical prediction may be measured by carefully designing experiments. Finally, discussions on the adiabatic representation, the PES construction, and possibility of the classical-dynamics solutions are given. Based on these discussions, a simple outlook on the dynamics of photocatalytics is finally given.

Sagatov, Nursultan E.; Gavryushkin, Pavel N.; Bekker, Tatyana B.; Litasov, Konstantin D.

doi: 10.1039/d2cp01846bpmid: 35766217

Based on ab initio molecular dynamic simulations, dynamic disorder of [BO3] groups in the Ba3(BO3)2 compound has been established. This is the first example of dynamic disorder in borates. It has been shown that static disorder of BO3 groups in the Ba3(BO3)2 crystals [Bekker et al., J. Am. Ceram. Soc., 2018, 101, 450] can be the result of quenching of dynamically disordered high-temperature modifications.

Liu, Yilin; Su, Jincai; Duan, Fei; Cui, Xin; Yan, Weichao; Jin, Liwen

doi: 10.1039/d2cp01411dpmid: 35708065

Hydrophilic nanocomposite membranes have significant advantages in the separation of water vapor which is the core process in air dehumidification. This paper focuses on exploring the micro-mechanism of enhanced separation using graphene oxide–polyvinyl alcohol (GO–PVA) nanocomposite membranes. The sorption and diffusion behaviors of water vapor and nitrogen in GO–PVA membranes were investigated using molecular dynamics (MD) and Monte Carlo (MC) methods. The study showed that embedding GO into a PVA matrix results in a higher glass transition temperature and fractional free volume. The latter is believed to enhance the diffusivity of gas molecules in polymeric membranes. The interaction between the polymer chains and GO nanoparticles notably promotes the adsorption capacity of water vapor and inhibits nitrogen adsorption in the membrane. A water vapor permeance of 8844.07 Barrer and a separation factor of 3.53 could be achieved with the GO–PVA-0.5 membrane. The analysis confirmed that GO has the same effect on single gas and binary gas mixtures, i.e., increasing the water vapor permeability and selectivity. The calculated water vapor permeance of binary gas is 83% lower than that of single gas permeation. It is expected that this research could provide fundamentals for the optimization and synthesis of gas separation membranes.

Nakatani, Kaho; Teshigawara, Sho; Tanahashi, Yuta; Kasahara, Kento; Higashi, Masahiro; Sato, Hirofumi

doi: 10.1039/d2cp01699kpmid: 35647764

Nitration of benzene is a representative aromatic substitution reaction related to the σ-complex (arenium ion or “Wheland” intermediate) concept. This reaction is typically carried out in a mixed acid solution to generate nitronium ions, and how solvent molecules play roles in the reaction has been of great interest. Here we will shed new light on the reaction, namely the electronic structure and the microscopic insights of the solvation, which have been rarely discussed so far. We studied this process using the reference interaction site model-self consistent field with constrained spatial electron density distribution (RISM-SCF-cSED) method, considering sulfuric acid or water molecules as a solvent. In this method, the electronic structure of the solute and the solvation structure are self-consistently determined based on quantum chemistry and statistical mechanics of molecular liquids. The solvation free energy surfaces in solution and solvation structures were verified. In the bond formation process of benzene and nitronium ions, the solvation structure by sulfuric acid molecules drastically changes and the solvation effect on the free energy is quite large. We revealed largely contributing resonance structures in the π-electron system of the σ-complex in gas and solution phases by analysing the valence electronic structures.

Li, Xiaoqing; Lindale, Jacob R.; Eriksson, Shannon L.; Warren, Warren S.

doi: 10.1039/d2cp00899hpmid: 35552575

SABRE (Signal Amplification by Reversible Exchange) methods provide a simple, fast, and cost-effective method to hyperpolarize a wide variety of molecules in solution, and have been demonstrated with protons and, more recently, with heteronuclei (X-SABRE). Here, we present several oscillating pulse sequences that use magnetic fields far away from the resonance condition of continuous excitation and can commonly triple the polarization. An analysis with average Hamiltonian theory indicates that the oscillating pulse, in effect, adjusts the J-couplings between hydrides and target nuclei and that a much weaker coupling produces maximum polarization. This theoretical treatment, combined with simulations and experiment, shows substantial magnetization improvements relative to traditional X-SABRE methods. It also shows that, in contrast to most pulse sequence applications, waveforms with reduced time symmetry in the toggling frame make magnetization generation more robust to experimental imperfections.

Kobayashi, Takeshi; Smiatek, Jens; Fyta, Maria

doi: 10.1039/d2cp01346kpmid: 35766260

Room temperature ionic liquid solutions confined between neutral and charged surfaces are investigated by means of atomistic Molecular Dynamics simulations. We study 1-ethyl-3-methylimidazolium dicyanamide ([EMIm]+[DCA]−) in water or dimethylsulfoxide (DMSO) mixtures in confinement between two interfaces. The analysis is based on the comparison of the molecular species involved and the charged state of the surfaces. Focus is given on the influence of different water/DMSO concentrations on the microstructuring and accumulation of each species. Thermodynamic aspects, such as the entropic contributions in the observed trends are obtained from the simulations using a lattice-gas theory. The results clearly underline the differences in these properties for the water and DMSO mixtures and unravel the underlying mechanisms and inherent details. We were able to pinpoint the importance of the size and the relative permittivity of the molecules in guiding their microstructuring in the vicinity of the surfaces, as well as their interactions with the latter, i.e. the solute–surface interactions. The influence of water and DMSO on the overscreening at charged interfaces is also discussed. The analysis on the molecular accumulation at the interfaces allows us to predict whether the accumulation is entropy or enthalpy driven, which has an impact in the removal of the molecular species from the surfaces. We discuss the impact of this work in providing an essential understanding towards a careful design of electrochemical elements.

Zang, Xiangyu; Zhang, Zhaoyan; Jiang, Shukang; Zhao, Yingqi; Wang, Tiantong; Wang, Chong; Li, Gang; Xie, Hua; Yang, Jiayue; Wu, Guorong; Zhang, Weiqing; Shu, Jinian; Fan, Hongjun; Yang, Xueming; Jiang, Ling

Sredojević, Dušan; Stavrić, Srđan; Lazić, Vesna; Ahrenkiel, S. Phillip; Nedeljković, Jovan M.

doi: 10.1039/d2cp02041fpmid: 35775978

The optical properties of surface-modified silver nanoparticles (Ag NPs) with aromatic amino acids tryptophan (Trp) and histidine (His) were examined using the cluster model for density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. Also, the redistribution of electronic charges upon chemisorption of ligand molecules onto silver's surfaces is determined. The obtained theoretical data, on one side, undoubtedly indicate the the formation of an interfacial charge transfer (ICT) complex between silver and this type of ligand, and, on the other side, partial oxidation of surface silver atoms accompanied by an increase of electron density in ligand molecules. The ICT complex formation, based on noble metal nanoparticles, has never been reported previously to the best of our knowledge. The experimental spectroscopic measurements support the theoretical data. A new absorption band in the visible spectral range appears upon surface modification of Ag NPs, and, when exposed to air, oxidation of surface-modified Ag NPs is significantly faster than the oxidation of the unmodified ones.