Previous work testing density functionals for use in calculating high-spin–low-spin energy differences, ΔEHL, for iron(II) spin-crossover transitions has tended to conclude that only properly reparametrized hybrid functionals can predict ΔEHL since it seems to depend critically on a correct description of the electron pairing energy governed by the exchange term. Exceptions to this rule are the previous three papers (I, II, and III in the present series of papers) where it was found that modern generalized gradient approximations (GGAs) and meta-GGAs could do as well as hybrid functionals, if not better, for this type of problem. In the present paper, we extend these previous studies to five more molecules which are too large to treat with high-quality ab initio calculations, namely, the series [Fe(L)(‘NHS4’)], where NHS4=2.2′-bis(2-mercaptophenylthio)diethylamine dianion, and L=NH3, N2H4, PMe3, CO, and NO+. Since we know of no reliable experimental estimate of ΔEHL, we content ourselves with a comparison against the experimentally determined ground-state spin symmetry including, in so far as possible, finite-temperature effects. Together with the results of Papers I, II, and III, this paper provides a test of a large number of functionals against the high-spin/low-spin properties of a diverse set of Fe(II) compounds, making it possible to draw some particulary interesting conclusions. Trends among different classes of functionals are discussed and it is pointed out that there is at least one functional, namely, the OLYP generalized gradient approximation, which is able to give a reasonably good description of the delicate spin energetics of Fe(II) coordination compounds without resorting to hybrid functionals which require the relatively more expensive calculation of a Hartree–Fock-type exchange term.

Applications of the Wang-Landau algorithm for simulating phase coexistence at fixed temperature are presented. The number density is sampled using either volume scaling or particle insertion/deletion. The resulting algorithms, while being conceptually easy, are of comparable efficiency to existing multicanonical methods but with the advantage that neither the chemical potential nor the pressure at phase coexistence has to be estimated in advance of the simulation. First, we benchmark the algorithm against literature results for the vapor-liquid transition in the Lennard-Jones fluid. We then demonstrate the general applicability of the algorithm by studying vapor-liquid coexistence in two examples of complex fluids: charged soft spheres, which exhibit a transition similar to that in the restricted primitive model of ionic fluids, being characterized by strong ion pairing in the vapor phase; and Stockmayer fluids with high dipole strengths, in which the constituent particles aggregate to form chains, and for which the very existence of a transition has been widely debated. Finally, we show that the algorithm can be used to locate a weak isotropic-nematic transition in a fluid of Gay-Berne mesogens.

High-performance composites based on basalt fibers are becoming increasingly available. However, in comparison to traditional composites containing glass or carbon fibers, their mechanical properties are currently less well known. In particular, this is the case for laminates consisting of unidirectional plies of continuous basalt fibers in an epoxy polymer matrix. Here, we report a full quasi-static characterization of the properties of such a material. To this end, we investigate tension, compression, and shear specimens, cut from quality autoclave-cured basalt composites. Our findings indicate that, in terms of strength and stiffness, unidirectional basalt fiber composites are comparable to, or better than epoxy composites made from E-glass fibers. At the same time, basalt fiber composites combine low manufacturing costs with good recycling properties and are therefore well suited to a number of engineering applications.

Vapor-liquid coexistence in fluids of charged hard dumbbells, each made up of two oppositely charged hard spheres with diameters σ and separation d, has been studied using grand-canonical Monte Carlo simulations. In the limit d∕σ→0, and with the temperature scaled accordingly, the system corresponds to dipolar hard spheres. For separations in the range 0.3<d∕σ⩽1 the coexisting vapor phase contains compact clusters. For separations in the range 0.1⩽d∕σ<0.3 the coexistence is between a chainlike vapor and a networklike liquid. Finite-size effects preclude the simulation of the coexistence in systems with d∕σ<0.1, but extrapolations of the results to d∕σ→0 yield estimates of the apparent critical parameters for dipolar hard spheres.

The question of whether a vapour–liquid phase transition exists in systems of particles with purely dipolar interactions is examined. New Monte Carlo simulation results are presented for the dipolar Yukawa hard sphere (DYHS) fluid with very small values of the attractive Yukawa well depth, almost two orders of magnitude smaller than the characteristic dipolar interaction energy. In this way, it is possible to approach the dipolar hard sphere (DHS) limit. It is found that phase separation is not observable beyond a critical value of the Yukawa energy parameter, even though in thermodynamic and structural terms, the DYHS and DHS systems are very similar. It is suggested that either some very subtle physics distinguishes the DYHS and DHS systems, or the observation of a phase transition in DHSs is precluded by finite-size effects.