Insight into CO2 dissociation in plasmas from numerical solution of a vibrational diffusion equation

The dissociation of CO2 molecules in plasmas is a subject of enormous importance for fundamental studies and the recent interest in carbon capture and carbon-neutral fuels. The vibrational excitation of the CO2 molecule plays an important role in the process. The complexity of the present state-to-state (STS) models makes it difficult to find out the key parameters. In this paper we propose as an alternative a numerical method based on the diffusion formalism developed in the past for analytical studies. The non-linear Fokker-Planck equation is solved by the time-dependent diffusion Monte Carlo method. Transport quantities are calculated from STS rate coefficients. The asymmetric stretching mode of CO2 is used as a test case. We show that the method reproduces the STS results or a Treanor distribution depending on the choice of the boundary conditions. A positive drift, whose energy onset is determined by the vibrational to translational temperature ratio, brings molecules from mid-energy range to dissociation. The high-energy fall of the distribution is observed even neglecting VT processes which are normally believed to be its cause. Our study explains several puzzling features of previous studies, provides new insights into the control of the dissociation rate and a much sought compression of the required data for modeling

Non-thermal photons and H2 formation in the early Universe

The cosmological recombination of H and He at z \sim 1000 and the formation of H2 during the dark ages produce a non-thermal photon excess in the Wien tail of the cosmic microwave background (CMB) blackbody spectrum. Here we compute the effect of these photons on the H- photodetachment and H2+ photodissociation processes. We discuss the implications for the chemical evolution of the Universe in the post-recombination epoch, emphasizing how important a detailed account of the full vibrational manifold of H2 and H2+ in the chemical network is. We find that the final abundances of H2, H2+, H3+ and HD are significantly smaller than in previous calculations that neglected the effect of non-thermal photons. The suppression is mainly caused by extra hydrogen recombination photons and could affect the formation rate of first stars. We provide simple analytical approximations for the relevant rate coefficients and briefly discuss the additional effect of dark matter annihilation on the considered reaction rates.Comment: 10 pages, 12 figures, 1 table; accepted for publication in MNRA

Particle propagation and electron transport in gases

In this review, we detail the commonality of mathematical intuitions that underlie three numerical methods used for the quantitative description of electron swarms propagating in a gas under the effect of externally applied electric and/or magnetic fields. These methods can be linked to the integral transport equation, following a common thread much better known in the theory of neutron transport than in the theory of electron transport. First, we discuss the exact solution of the electron transport problem using Monte Carlo (MC) simulations. In reality we will progress much further, showing the interpretative role that the diagrams used in quantum theory and quantum field theory can play in the development of MC. Then, we present two methods, the Monte Carlo Flux and the Propagator method, which have been developed at this moment. The first one is based on a modified MC method, while the second shows the advantage of explicitly applying the mathematical idea of propagator to the transport problem.Comment: Review paper, 46 pages, 4 figure

The unbiased Diffusion Monte Carlo: a versatile tool for two-electron systems confined in different geometries

Computational codes based on the Diffusion Monte Carlo method can be used to determine the quantum state of two-electron systems confined by external potentials of various nature and geometry. In this work, we show how the application of this technique in its simplest form, that does not employ complex analytic guess functions, allows to obtain satisfactory results and, at the same time, to write programs that are readily adaptable from one type of confinement to another. This adaptability allows an easy exploration of the many possibilities in terms of both geometry and structure of the system. To illustrate these results, we present calculations in the case of two-electron hydrogen-based species (H$_2$ and H$_3^+$) and two different types of confinement, nanotube-like and octahedral crystal-field