The mononuclear Mn(CO)(5)X and binuclear Mn(2)(CO)(8)(μ-X)(2) manganese carbonyl halides have long been known for the halogens Cl, Br, and I. However, the corresponding manganese carbonyl fluorides (X = F) remain unknown. The structures and thermochemistry of such manganese carbonyl fluorides and their decarbonylation products have now been investigated using density functional theory. In all c...

Fire is a complex natural phenomena involving chemical reactions and turbulent flow of hot gaseous products. Significant computer graphics research is devoted to modelling the turbulent dynamics of fire; however flicker which results from the chemical nature of fire has not been previously modelled. In this paper we present a technique that addresses both modelling of dynamics and chemical aspe...

Basis set convergence of correlation effects on molecular atomization energies beyond the coupled cluster with singles and doubles (CCSD) approximation has been studied near the one-particle basis set limit. Quasiperturbative connected triple excitations, (T), converge more rapidly than L(-3) (where L is the highest angular momentum represented in the basis set), while higher-order connected tr...

High-flux optical systems (HFOSs) are optical concentrators used to increase the radiative flux of the natural terrestrial solar irradiation. High radiative flux concentration leads to high energy density in solar receivers which allows to obtain high temperatures. In solar thermochemical applications, the hightemperature heat drives endothermic thermochemical reactions. HFOSs have been deploye...

Recent calculations by Montgomery and co-workers’ suggest that the accepted value for the heat of formation of COF, is in error by more than 6 kcal mol-’. Additional calculations reported here support this contention. The revised value for A ~ H ~ ~ ~ B ( C O F ~ ) permits a reanalysis of available kinetic and thermodynamic data on the energies of a number of other small fluorine-containing mol...

The calculation of thermochemical data requires accurate molecular energies and heat capacities. Traditional methods rely upon the standard harmonic normal-mode analysis to calculate the vibrational and rotational contributions. We utilize path-integral Monte Carlo for going beyond the harmonic analysis and to calculate the vibrational and rotational contributions to ab initio energies. This is...

The linear generalized equation described in this paper provides a further dimension to the prediction of lattice potential energies/enthalpies of ionic solids. First, it offers an alternative (and often more direct) approach to the well-established Kapustinskii equation (whose capabilities have also recently been extended by our recent provision of an extended set of thermochemical radii). Sec...