Search

Hydrocarbon pyrolysis is a complex process involving large numbers of chemical species and types of chemical reactions. Its quantitative description is important for planetary sciences, in particular, for understanding the processes occurring in the interior of icy planets, such as Uranus and Neptune, where small hydrocarbons are subjected to high temperature and pressure. We propose a computationally cheap methodology based on an originally developed ten-reaction model and the configurational model from random graph theory. This methodology generates accurate predictions for molecule size distributions for a variety of initial chemical compositions and temperatures ranging from 3200 to 5000 K. Specifically, we show that the size distribution of small molecules is particularly well predicted, and the size of the largest molecule can be accurately predicted provided that this molecule is not too large. [ABSTRACT FROM AUTHOR]

We develop computational tools for spectral analysis of stochastic networks representing energy landscapes of atomic and molecular clusters. Physical meaning and some properties of eigenvalues, left and right eigenvectors, and eigencurrents are discussed. We propose an approach to compute a collection of eigenpairs and corresponding eigencurrents describing the most important relaxation processes taking place in the system on its way to the equilibrium. It is suitable for large and complex stochastic networks where pairwise transition rates, given by the Arrhenius law, vary by orders of magnitude. The proposed methodology is applied to the network representing the Lennard-Jones- 38 cluster created by Wales's group. Its energy landscape has a double funnel structure with a deep and narrow face-centered cubic funnel and a shallower and wider icosahedral funnel. However, the complete spectrum of the generator matrix of the Lennard-Jones-38 network has no appreciable spectral gap separating the eigenvalue corresponding to the escape from the icosahedral funnel. We provide a detailed description of the escape process from the icosahedral funnel using the eigencurrent and demonstrate a superexponential growth of the corresponding eigenvalue. The proposed spectral approach is compared to the methodology of the Transition Path Theory. Finally, we discuss whether the Lennard-Jones-38 cluster is metastable from the points of view of a mathematician and a chemical physicist, and make a connection with experimental works. [ABSTRACT FROM AUTHOR]