arXiv subjects

P. del Mazo-Sevillano

Publications and source records attributed to P. del Mazo-Sevillano.

3 recordsLinked to original sources

arXiv2026

Searching for the elusive CH2+ with the James Webb Space Telescope. Another carbocation to constrain astrochemical networks

Carbocations are key species in interstellar chemistry, providing entry points for building larger hydrocarbons. CH+, and more recently, CH3+, have been detected. Other carbocations await detection to provide a comprehensive view of the astrochemical network that is at work in the interstellar medium. We search for CH2+ in objects in which CH3+ was detected and evaluate the most favorable conditions for detecting the elusive CH2+ reactive cation. We calculated the CH2+ rotational and rovibrational transitions expected to contribute in the mid- to far-infrared, focusing on the lower-energy rovibrational levels. We then calculated CH2+ infrared emission spectra at different excitation temperatures and compared them to JWST spectra of the externally irradiated disk d203-506 in Orion, where CH+ and CH3+ have already been detected. We used thermochemical models to predict the abundance and spatial morphology of CH2+ to better understand its nondetection. The comparison to JWST spectra allowed us to provide excitation-temperature-dependent upper limits to the excited column density. These are several times lower than those detected for CH+ and CH3+ in their excited states. Based on model calculations for photodissociation regions and assuming similar excitation temperatures, the upper limit derived from observations and CH2+ model spectrum is either slightly above or below the column density expected from models of photodissociation regions. We provide a list of tabulated transitions to allow the community to search for this carbocation in future observations as CH2+ is key in providing observational constraints on astrochemical models.

astro-ph.GA↗

arXiv2023

Variational principle to regularize machine-learned density functionals: the non-interacting kinetic-energy functional

Practical density functional theory (DFT) owes its success to the groundbreaking work of Kohn and Sham that introduced the exact calculation of the non-interacting kinetic energy of the electrons using an auxiliary mean-field system. However, the full power of DFT will not be unleashed until the exact relationship between the electron density and the non-interacting kinetic energy is found. Various attempts have been made to approximate this functional, similar to the exchange--correlation functional, with much less success due to the larger contribution of kinetic energy and its more non-local nature. In this work we propose a new and efficient regularization method to train density functionals based on deep neural networks, with particular interest in the kinetic-energy functional. The method is tested on (effectively) one-dimensional systems, including the hydrogen chain, non-interacting electrons, and atoms of the first two periods, with excellent results. For the atomic systems, the generalizability of the regularization method is demonstrated by training also an exchange--correlation functional, and the contrasting nature of the two functionals is discussed from a machine-learning perspective.

physics.chem-ph↗

arXiv2023

Vibrational, non-adiabatic and isotopic effects in the dynamics of the H$_2$ + H$_2^+$ $\rightarrow$ H$_3^+$ + H reaction: application to plasma modeling

The title reaction is studied using a quasi-classical trajectory method for collision energies between 0.1 meV and 10 eV, considering the vibrational excitation of H$_2^+$ reactant. A new potential energy surface is developed based on a Neural Network many body correction of a triatomics-in-molecules potential, which significantly improves the accuracy of the potential up to energies of 17 eV, higher than in other previous fits.The effect of the fit accuracy and the non-adiabatic transitions on the dynamics are analyzed in detail.The reaction cross section for collision energies above 1 eV increases significantly with the increasing of the vibrational excitation of H$_2^+$($v'$), for values up to $v'$=6. The total reaction cross section (including the double fragmentation channel) obtained for $v'$=6 matches the new experimental results obtained by Savic, Schlemmer and Gerlich [Chem. Phys. Chem. 21 (13), 1429.1435(2020)]. The differences among several experimental setups, for collision energies above 1 eV, showing cross sections scattered/dispersed over a rather wide interval, can be explained by the differences in the vibrational excitations obtained in the formation of H$_2^+$ reactants. On the contrary, for collision energies below 1 eV, the cross section is determined by the long range behavior of the potential and do not depend strongly on the vibrational state of H$_2^+$. In addition in this study, the calculated reaction cross sections are used in a plasma model and compared with previous results. We conclude that the efficiency of the formation of H$_3^+$ in the plasma is affected by the potential energy surface used.

physics.chem-ph↗