We reformulate Rosenfeld's fundamental-measure theory using the excess Helmholtz energy density from the Boublik-Mansoori-Carnahan-Starling-Leland equation of state instead of that from the scaled-particle theory. The new density functional theory yields improved density distributions, especially the contact densities, of inhomogeneous hard-sphere fluids as well as more accurate direct and pair correlation functions of homogeneous hard spheres including those of highly asymmetric mixtures. This new density functional theory will provide an accurate reference for the further development of a statistical-thermodynamic theory of complex fluids at uniform and at inhomogeneous conditions.

A new density functional theory is developed for inhomogeneous mixtures of polymeric fluids by combining Rosenfeld’s fundamental-measure theory for excluded volume effects with Wertheim’s first-order thermodynamic perturbation theory for chain connectivity. With no adjustable parameters, theoretical predictions are in excellent agreement with Monte Carlo simulation data for the density distributions and for the adsorption isotherms of hard-sphere chains near hard walls or in slit-like pores. This theory is applied to calculate the force between two parallel hard walls separated by hard-sphere chains at different densities. Calculated results indicate that the chain-mediated force is attractive and decays monotonically with separation at low chain densities, it oscillates at high chain densities and in between, it is attractive at small separation and repulsive at large separation. This new density functional theory is simpler than similar theories in the literature and is directly applicable to mixtures.

The fundamental-measure theory ͑FMT͒ of Rosenfeld for hard spheres is extended to inhomogeneous associating fluids on the basis of Wertheim's first-order thermodynamic perturbation theory ͑TPT1͒. The excess intrinsic Helmholtz energy, which includes contributions from hard-sphere repulsion and from intermolecular bonding, is represented as a functional of three weighted densities that are related to the geometry of spherical particles. In the absence of association, this theory is the same as the original FMT, and at bulk conditions it reduces to TPT1. In comparison with Monte Carlo simulation results, the extended fundamental-measure theory provides good descriptions of the density profiles and adsorption isotherms of associating hard spheres near a hard wall. Calculated results indicate that the critical temperatures for the vaporliquid equilibria of associating fluids in hard slit pores are suppressed compared with that for the bulk fluid and the confinement has more significant impact on the liquid side than the vapor side of the coexistence curve. Unlike nonpolar fluids at similar conditions, saturated associating liquids in hard slit pores do not exhibit strong layering near the solid surface.

Sodium storage capacity, mobility, and volume change during sodiation on the surfaces of interlayer-expanded Ti3C2 MXenes are investigated using ab initio density functional theory. The theoretical results reveal that the interlayer-expanded bare, F-, O-, and OH-functionalized Ti3C2 MXenes exhibit low barriers for sodium diffusion and small changes of lattice constant during sodiation. In addition, enlarged interlayer distance enables the stable multilayer adsorption on the bare and O-functionalized Ti3C2 MXenes and therefore significantly enhances their theoretical capacities. Both bare and O-functionalized Ti3C2 MXenes are predicted to be prospective anode materials for sodium-ion batteries with high theoretical capacities, fast discharge/charge rates, and good cycling performances. The present results provide a new route to improve the battery performances of anode materials based on MXene intercalation hosts.

The electronic and adsorption properties of graphene can be changed significantly through substitutional doping with nitrogen and nitrogen decoration of vacancies. Here ab initio density functional theory with a dispersion correction was used to investigate the stability, magnetic and adsorption properties of nine defects in graphene, including both nitrogen substitutional doping and nitrogen decoration of vacancies. The results indicate that only pyridinic N2V2 defect in graphene shows a ferromagnetic spin structure with high magnetic moment and magnetic stabilization energy. Not all nitrogen-doped defects can improve the capacity of the lithium-ion batteries. The adsorption energies of a lithium atom on nitrogen-substituted graphenes are more positive, indicating that they are meta-stable and no better than the pristine graphene as anode materials of lithium-ion batteries. Nitrogen-decorated single and double vacancy defects, especially for the pyridinic N2V2 defect in graphene, can greatly improve the reversible capacity of the battery in comparison with the pristine graphene. The theoretical prediction of the reversible capacity of the battery is 1039 mA h g(-1) for the nitrogen-doped graphene material synthesized by Wu et al., which is in good agreement with the experimental data (1043 mA h g(-1)). The theoretical computations suggest that nitrogen-decorated single and double vacancy defects in graphene are the promising candidate for anode materials of lithium-ion batteries. Each nitrogen atom in the decoration can improve the reversible capacity of the battery by 63.3-124.5 mA h g(-1) in a 4 × 4 supercell of graphene. The present work provides crucial information for the development of N-doped graphene-based anode materials of lithium-ion batteries.