arXiv subjects

R. C. Forrey

Publications and source records attributed to R. C. Forrey.

15 recordsLinked to original sources

arXiv2024

Inelastic Triatom-Atom Quantum Close-Coupling Dynamics in Full Dimensionality: all rovibrational mode quenching of water due to H impact on a six-dimensional potential energy surface

The rovibrational level populations, and subsequent emission in various astrophysical environments, is driven by inelastic collision processes. The available rovibrational rate coefficients for water have been calculated using a number of approximations. We present a numerically exact calculation for the rovibrational quenching for all water vibrational modes due to collisions with atomic hydrogen. The scattering theory implements a quantum close-coupling (CC) method on a high level ab initio six-dimensional (6D) potential energy surface (PES). Total rovibrational quenching cross sections for excited bending levels were compared with earlier results on a 4D PES with the rigid-bender close-coupling (RBCC) approximation. General agreement between 6D-CC and 4D-RBCC calculations are found, but differences are evident including the energy and amplitude of low-energy orbiting resonances. Quenching cross sections from the symmetric and asymmetric stretch modes are provided for the first time. The current 6D-CC calculation provides accurate inelastic data needed for astrophysical modeling.

astro-ph.GA↗

arXiv2020

Revisiting the Formation of HeH$^+$ in the Planetary Nebula NGC 7027

From four independent calculations using three different theoretical approaches, rate coefficients for the formation of HeH$^+$ via the radiative association of He$^+$ and H were computed. Good agreement is found between our new calculations and prior results obtained two decades ago for kinetic temperatures between $\sim$800 and 20,000 K. This finding is inconsistent with a recent claim in the literature of a wide variation in published values and establishes the robustness of our knowledge of this process for the formation of HeH$^+$. The implications of the current results to the first detection of HeH$^+$ and its modeled abundance in the planetary nebula NGC 7027 are discussed.

astro-ph.GA↗

arXiv2020

Machine-learning-corrected quantum dynamics calculations

Quantum scattering calculations for all but low-dimensional systems at low energies must rely on approximations. All approximations introduce errors. The impact of these errors is often difficult to assess because they depend on the Hamiltonian parameters and the particular observable under study. Here, we illustrate a general, system and approximation-independent, approach to improve the accuracy of quantum dynamics approximations. The method is based on a Bayesian machine learning (BML) algorithm that is trained by a small number of rigorous results and a large number of approximate calculations, resulting in ML models that accurately capture the dependence of the dynamics results on the quantum dynamics parameters. Most importantly, the present work demonstrates that the BML models can generalize quantum results to different dynamical processes. Thus, a ML model trained by a combination of approximate and rigorous results for a certain inelastic transition can make accurate predictions for different transitions without rigorous calculations. This opens the possibility of improving the accuracy of approximate calculations for quantum transitions that are out of reach of rigorous scattering calculations.

physics.chem-ph↗

arXiv2018

Full-dimensional Quantum Dynamics of SiO in Collision with H$_2$

We report the first full-dimensional potential energy surface (PES) and quantum mechanical close-coupling calculations for scattering of SiO due to H$_2$. The full-dimensional interaction potential surface was computed using the explicitly correlated coupled-cluster (CCSD(T)-F12b) method and fitted using an invariant polynomial approach. Pure rotational quenching cross sections from initial states $v_1=0$, $j_1$=1-5 of SiO in collision with H$_2$ are calculated for collision energies between 1.0 and 5000 cm$^{-1}$. State-to-state rotational rate coefficients are calculated at temperatures between 5 and 1000 K. The rotational rate coefficients of SiO with para-H$_2$ are compared with previous approximate results which were obtained using SiO-He PESs or scaled from SiO-He rate coefficients. Rovibrational state-to-state and total quenching cross sections and rate coefficients for initially excited SiO($v_1=1, j_1$=0 and 1) in collisions with para-H$_2$($v_2=0,j_2=0$) and ortho-H$_2$($v_2=0,j_2=1$) were also obtained. The application of the current collisional rate coefficients to astrophysics is briefly discussed.

physics.chem-ph↗

arXiv2017

Rate constants for the formation of SiO by radiative association

Accurate molecular data for the low-lying states of SiO are computed and used to calculate rate constants for radiative association of Si and O. Einstein A-coefficients are also calculated for transitions between all of the bound and quasi-bound levels for each molecular state. The radiative widths are used together with elastic tunneling widths to define effective radiative association rate constants which include both direct and indirect (inverse predissociation) formation processes. The indirect process is evaluated for two kinetic models which represent limiting cases for astrophysical environments. The first case scenario assumes an equilibrium distribution of quasi-bound states and would be applicable whenever collisional and/or radiative excitation mechanisms are able to maintain the population. The second case scenario assumes that no excitation mechanisms are available which corresponds to the limit of zero radiation temperature and zero atomic density. Rate constants for SiO formation in realistic astrophysical environments would presumably lie between these two limiting cases.

astro-ph.IM↗

arXiv2015

Quantum Calculation of Inelastic CO Collisions with H. II. Pure Rotational Quenching of High Rotational Levels

Carbon monoxide is a simple molecule present in many astrophysical environments, and collisional excitation rate coefficients due to the dominant collision partners are necessary to accurately predict spectral line intensities and extract astrophysical parameters. We report new quantum scattering calculations for rotational deexcitation transitions of CO induced by H using the three-dimensional potential energy surface~(PES) of Song et al. (2015). State-to-state cross sections for collision energies from 10$^{-5}$ to 15,000~cm$^{-1}$ and rate coefficients for temperatures ranging from 1 to 3000~K are obtained for CO($v=0$, $j$) deexcitation from $j=1-45$ to all lower $j'$ levels, where $j$ is the rotational quantum number. Close-coupling and coupled-states calculations were performed in full-dimension for $j$=1-5, 10, 15, 20, 25, 30, 35, 40, and 45 while scaling approaches were used to estimate rate coefficients for all other intermediate rotational states. The current rate coefficients are compared with previous scattering results using earlier PESs. Astrophysical applications of the current results are briefly discussed.

astro-ph.GA↗

arXiv2015

Collisional quenching of highly rotationally excited HF

Collisional excitation rate coefficients play an important role in the dynamics of energy transfer in the interstellar medium. In particular, accurate rotational excitation rates are needed to interpret microwave and infrared observations of the interstellar gas for nonlocal thermodynamic equilibrium line formation. Theoretical cross sections and rate coefficients for collisional deexcitation of rotationally excited HF in the vibrational ground state are reported. The quantum-mechanical close-coupling approach implemented in the nonreactive scattering code MOLSCAT was applied in the cross section and rate coefficient calculations on an accurate 2D HF-He potential energy surface. Estimates of rate coefficients for H and H$_2$ colliders were obtained from the HF-He collisional data with a reduced-potential scaling approach. The calculation of state-to-state rotational quenching cross sections for HF due to He with initial rotational levels up to $j=20$ were performed for kinetic energies from 10$^{-5}$ to 15000 cm$^{-1}$. State-to-state rate coefficients for temperatures between 0.1 and 3000 K are also presented. The comparison of the present results with previous work for lowly-excited rotational levels reveals significant differences. In estimating HF-H$_2$ rate coefficients, the reduced-potential method is found to be more reliable than the standard reduced-mass approach. The current state-to-state rate coefficient calculations are the most comprehensive to date for HF-He collisions. We attribute the differences between previously reported and our results to differences in the adopted interaction potential energy surfaces. The new He rate coefficients can be used in a variety of applications. The estimated H$_2$ and H collision rates can also augment the smaller datasets previously developed for H$_2$ and electrons.

astro-ph.SR↗

arXiv2015

Quantum dynamics of CO-H$_2$ in full dimensionality

Accurate rate coefficients for molecular vibrational transitions due to collisions with H$_2$, critical for interpreting infrared astronomical observations, are lacking for most molecules. Quantum calculations are the primary source of such data, but reliable values that consider all internal degrees of freedom of the collision complex have only been reported for H$_2$-H$_2$ due to the difficulty of the computations. Here we present essentially exact full-dimensional dynamics computations for rovibrational quenching of CO due to H$_2$ impact. Using a high-level six-dimensional potential surface, time-independent scattering calculations, within a full angular-momentum-coupling formulation, were performed for the deexcitation of vibrationally excited CO. Agreement with experimentally-determined results confirms the accuracy of the potential and scattering computations, representing the largest of such calculations performed to date. This investigation advances computational quantum dynamics studies representing initial steps toward obtaining CO-H$_2$ rovibrational quenching data needed for astrophysical modeling.

astro-ph.SR↗

arXiv2014

On the Validity of Collider-Mass Scaling for Molecular Rotational Excitation

Rate coefficients for collisional processes such as rotational and vibrational excitation are essential inputs in many astrophysical models. When rate coefficients are unknown, they are often estimated using known values from other systems. The most common example is to use He-collider rate coefficients to estimate values for other colliders, typically H$_2$, using scaling arguments based on the reduced mass of the collision system. This procedure is often justified by the assumption that the inelastic cross section is independent of the collider. Here we explore the validity of this approach focusing on rotational inelastic transitions for collisions of H, para-H$_2$, $^3$He, and $^4$He with CO in its vibrational ground state. We compare rate coefficients obtained via explicit calculations to those deduced by standard reduced-mass scaling. Not surprisingly, inelastic cross sections and rate coefficients are found to depend sensitively on both the reduced mass and the interaction potential energy surface. We demonstrate that standard reduced-mass scaling is not valid on physical and mathematical grounds, and as a consequence, the common approach of multiplying a rate coefficient for a molecule-He collision system by the constant factor of ~1.4 to estimate the rate coefficient for para-H$_2$ collisions is deemed unreliable. Furthermore, we test an alternative analytic scaling approach based on the strength of the interaction potential and the reduced mass of the collision systems. Any scaling approach, however, may be problematic when low-energy resonances are present; explicit calculations or measurements of rate coefficients are to be preferred.

astro-ph.GA↗

arXiv2013

Quantum Calculation of Inelastic CO Collisions with H: I. rotational quenching of low-lying rotational levels

New quantum scattering calculations for rotational deexcitation transitions of CO induced by H collisions using two CO-H potential energy surfaces (PESs) from Shepler et al. (2007) are reported. State-to-state rate coefficients are computed for temperatures ranging from 1 to 3000 K for CO($v=0,j$) deexcitation from $j=1-5$ to all lower $j^\prime$ levels, with $j$ being the rotational quantum number. Different resonance structures in the cross sections are attributed to the differences in the anisotropy and the long-range van der Waals well depths of the two PESs. These differences affect rate coefficients at low temperatures and give an indication of the uncertainty of the results. Significant discrepancies are found between the current rate coefficients and previous results computed using earlier potentials, while the current results satisfy expected propensity rules. Astrophysical applications to modeling far infrared and submillimeter observations are briefly discussed.

astro-ph.SR↗

arXiv2010

Rotational quenching of CO due to H$_2$ collisions

Rate coefficients for state-to-state rotational transitions in CO induced by both para- and ortho-H$_2$ collisions are presented. The results were obtained using the close-coupling method and the coupled-states approximation, with the CO-H$_2$ interaction potential of Jankowski & Szalewicz (2005). Rate coefficients are presented for temperatures between 1 and 3000 K, and for CO($v=0,j$) quenching from $j=1-40$ to all lower $j^\prime$ levels. Comparisons with previous calculations using an earlier potential show some discrepancies, especially at low temperatures and for rotational transitions involving large $|Δj|$. The differences in the well depths of the van der Waals interactions in the two potential surfaces lead to different resonance structures in the energy dependence of the cross sections which influence the low temperature rate coefficients. Applications to far infrared observations of astrophysical environments are briefly discussed.

astro-ph.SR↗

arXiv2008

Rotational quenching rate coefficients for H_2 in collisions with H_2 from 2 to 10,000 K

Rate coefficients for rotational transitions in H_2 induced by H_2 impact are presented. Extensive quantum mechanical coupled-channel calculations based on a recently published (H_2)_2 potential energy surface were performed. The potential energy surface used here is presumed to be more reliable than surfaces used in previous work. Rotational transition cross sections with initial levels J <= 8 were computed for collision energies ranging between 0.0001 and 2.5 eV, and the corresponding rate coefficients were calculated for the temperature range 2 < T <10,000 K. In general, agreement with earlier calculations, which were limited to 100-6000 K, is good though discrepancies are found at the lowest and highest temperatures. Low-density-limit cooling functions due to para- and ortho-H_2 collisions are obtained from the collisional rate coefficients. Implications of the new results for non-thermal H_2 rotational distributions in molecular regions are also investigated.

astro-ph↗

arXiv2006

State-to-state rotational transitions in H$_2$+H$_2$ collisions at low temperatures

We present quantum mechanical close-coupling calculations of collisions between two hydrogen molecules over a wide range of energies, extending from the ultracold limit to the super-thermal region. The two most recently published potential energy surfaces for the H$_2$-H$_2$ complex, the so-called DJ (Diep and Johnson, 2000) and BMKP (Boothroyd et al., 2002) surfaces, are quantitatively evaluated and compared through the investigation of rotational transitions in H$_2$+H$_2$ collisions within rigid rotor approximation. The BMKP surface is expected to be an improvement, approaching chemical accuracy, over all conformations of the potential energy surface compared to previous calculations of H$_2$-H$_2$ interaction. We found significant differences in rotational excitation/de-excitation cross sections computed on the two surfaces in collisions between two para-H$_2$ molecules. The discrepancy persists over a large range of energies from the ultracold regime to thermal energies and occurs for several low-lying initial rotational levels. Good agreement is found with experiment (Maté et al., 2005) for the lowest rotational excitation process, but only with the use of the DJ potential. Rate coefficients computed with the BMKP potential are an order of magnitude smaller.

physics.atom-ph↗

arXiv2004

Close-coupling calculations of low-energy inelastic and elastic processes in $^4$He collisions with H$_2$: A comparative study of two potential energy surfaces

The two most recently published potential energy surfaces (PESs) for the HeH$_2$ complex, the so-called MR (Muchnick and Russek) and BMP (Boothroyd, Martin, and Peterson) surfaces, are quantitatively evaluated and compared through the investigation of atom-diatom collision processes. The BMP surface is expected to be an improvement, approaching chemical accuracy, over all conformations of the PES compared to that of the MR surface. We found significant differences in inelastic rovibrational cross sections computed on the two surfaces for processes dominated by large changes in target rotational angular momentum. In particular, the H$_2$($ν=1, j=0$) total quenching cross section computed using the BMP potential was found to be a factor of $~$1000 larger than that obtained with the MR surface.

astro-ph↗

arXiv1999

Rate coefficients for rovibrational transitions in H_2 due to collisions with He

We present quantum mechanical and quasiclassical trajectory calculations of cross sections for rovibrational transitions in ortho- and para-H_2 induced by collisions with He atoms. Cross sections were obtained for kinetic energies between 10^-4 and 3 eV, and the corresponding rate coefficients were calculated for the temperature range 100<T<4000 K. Comparisons are made with previous calculations.

astro-ph↗