Searcharxiv⌕ Search

arXiv subjects

Otoniel Denis-Alpizar

Publications and source records attributed to Otoniel Denis-Alpizar.

4 recordsLinked to original sources

Predicted state-to-state collisional rate coefficients from neural networks

Molecular spectra observed in the interstellar medium are commonly analyzed using non-local thermodynamic equilibrium models, which requires accurate state-to-state collisional rate coefficients. Close-coupling calculations become prohibitively expensive for transitions from highly excited rotational states, therefore available datasets are often truncated at low initial states and temperatures; and since each new system also requires an accurate ab initio potential energy surface, many detected molecules have no collisional data. We employ two machine learning strategies to predict rotational state-to-state rate coefficients of molecules included in the train set beyond the range of initial states and temperatures computed so far, and predicting those of a molecule absent from training and validation sets. Feed-forward neural networks are trained on state-to-state de-excitation rate coefficients of 24 linear molecules colliding with para-H2. Scheme 1 includes all systems in the train+validation set, with 70%, 80%, and 90% initial-state boundaries and a 90% temperature boundary. Scheme 2 is trained on 22 systems described only by transition and molecular properties, and predicts two excluded systems, CS and CF+, whose astrophysical impact is explored with non-LTE calculations. For the 90% boundary, Scheme 1 predicts 99.4% of the test transitions within a factor of 2, and no prediction deviates from the reference value by more than a factor of 4.7. This model was used to complete 18 datasets. Scheme 2 reproduces the rate coefficients of two excluded systems within a factor of 3 for more than 92% of their transitions. Both schemes provide near-instantaneous complements to close-coupling calculations: Scheme 1 extends the range of a molecule already included in the training set with high accuracy, while Scheme 2 gives a reasonable first estimate for a molecule that has not been studied.

astro-ph.GA↗

Applying R-Matrix Theory to Atom-Molecule Inelastic Collisions: the case study of H$_2$O + H

The present study presents a comprehensive theoretical investigation of atom and asymmetric top molecule inelastic scattering based on the R-matrix formalism. The proposed methodology establishes a rigorous framework for treating inelastic collisions in the space-fixed coordinate system. The excellent numerical performance of the method is demonstrated through the comparison of state-to-state rotationally inelastic R-matrix cross sections for the H + H$_2$O system with those obtained using conventional close-coupling (CC) theory. The R-matrix approach is shown to deliver results of comparable accuracy while achieving substantially reduced computation times. The method is furthermore shown to achieve more than one order-of-magnitude speedup by exploiting GPU-accelerated diagonalisation through the MAGMA library. This combination of accuracy and computational efficiency positions the R--matrix approach as a powerful and scalable tool for investigating inelastic scattering involving complex polyatomic systems, thereby paving the way for systematic studies of molecule-molecule interactions in astrophysical, atmospheric, and cold-matter environments.

physics.chem-ph↗

Ro-vibrational relaxation of HCN in collisions with He: Rigid bender treatment of the bending-rotation interaction

We present a new theoretical method to treat atom-rigid bender inelastic collisions at the Close Coupling level (RBCC) in the space fixed frame. The coupling between rotation and bending is treated exactly within the rigid bender approximation and we obtain the cross section for the rotational transition between levels belonging to different bending levels. The results of this approach are compared with those obtained when using the rigid bender averaged approximation (RBAA) introduced in our previous work dedicated to this system. We discuss the validity of this approximation and of the previous studies based on rigid linear HCN.

physics.chem-ph↗

A four-dimensional potential energy surface for the He - HCN complex

A four-dimensional potential energy surface for the interaction between He and HCN with vibrational bending is presented. Ab initio calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and mid-bond functions. An accurate fit to the Ab-initio data has been obtained with a parametrized functional form. The global minimum is found in the linear He-HCN configuration with the H atom pointing towards Helium at the intermolecular separation of 7.94 a0. The corresponding well depth is 30.35 cm^-1 . The quality of the new potential has been tested by performing two comparisons with previous theoretical and experimental works. First, the rovibrational energy levels of the He-HCN complex for a linear configuration of the HCN molecule have been calculated. The dissociation energy is 8.99 cm^-1, which is slightly smaller than the semi-empirical value of 9.42 cm^-1 . The transitions frequencies are found to be in good agreement with the experimental data. Second, we performed close coupling calculations of the rotational de-excitation of HCN in collisions with He and observed a close similarity with the theoretical data published in a recent study.

physics.chem-ph↗