Showing papers by "Jonathan Tennyson published in 2023"

Foundations of plasma standards

Abstract: The field of low-temperature plasmas (LTPs) excels by virtue of its broad intellectual diversity, interdisciplinarity and range of applications. This great diversity also challenges researchers in communicating the outcomes of their investigations, as common practices and expectations for reporting vary widely in the many disciplines that either fall under the LTP umbrella or interact closely with LTP topics. These challenges encompass comparing measurements made in different laboratories, exchanging and sharing computer models, enabling reproducibility in experiments and computations using traceable and transparent methods and data, establishing metrics for reliability, and in translating fundamental findings to practice. In this paper, we address these challenges from the perspective of LTP standards for measurements, diagnostics, computations, reporting and plasma sources. This discussion on standards, or recommended best practices, and in some cases suggestions for standards or best practices, has the goal of improving communication, reproducibility and transparency within the LTP field and fields allied with LTPs. This discussion also acknowledges that standards and best practices, either recommended or at some point enforced, are ultimately a matter of judgment. These standards and recommended practices should not limit innovation nor prevent research breakthroughs from having real-time impact. Ultimately, the goal of our research community is to advance the entire LTP field and the many applications it touches through a shared set of expectations.

A regression model for plasma reaction kinetics

Abstract: Machine learning (ML) is used to provide reactions rates appropriate for models of low temperature plasmas with a focus on A + B → C + D binary chemical reactions. The regression model is trained on data extracted from the QBD, KIDA, NFRI and UfDA databases. The regression model used a variety of data on the reactant and product species, some of which also had to be estimated using ML. The final model is a voting regressor comprising three distinct optimized regression models: a support vector regressor, random forest regressor and a gradient-boosted trees regressor model; this model is made freely available via a GitHub repository. As a sample use case, the ML results are used to augment the chemistry of a BCl3/H2 gas mixture.

Electron scattering on molecular nitrogen: common gas, uncommon cross sections

Abstract: Abstract We discuss peculiar features of electron scattering on the N 2 molecule and the N 2 + ion, that are important for modeling plasmas, Earth’s and other planets’ atmospheres. These features are, among others: the resonant enhancement of the vibrational excitation in the region of the shape resonance around 2.4 eV, the resonant character of some of electronic excitation channels (and high values of these cross sections, both for triplet and singlet states), high cross section for the dissociation into neutrals, high cross sections for elastic scattering (and electronic transitions) on metastable states. For the N 2 + ion we discuss both dissociation and the dissociative ionization, leading to the formation of atoms in excited states, and dissociative recombination which depends strongly on the initial vibrational state of the ion. We conclude that the theory became an indispensable completion of experiments, predicting many of partial cross sections and their physical features. We hope that the data presented will serve to improve models of nitrogen plasmas and atmospheres. Graphical abstract

Identifying molecules with high electrical strength

Abstract: A search is conducted for possible gases with high electrical strength which could replace the widely used SF6 which has high global warming potential (GWP). The possible electrical strength of a molecule is assessed on the basis of low-energy electron collisions with low-energy resonances or weakly bound states taken as a possible indicator of high electrical strength. At the same time the energy of the highest occupied molecular orbital (HOMO) is used to assess the molecules’ GWP. A total of 62 small flourocarbon molecules are considered allowing the influence of different molecular structures (double bonded, triple bonded and cyclic) and the inclusion of different elements (hydrogen, nitrogen and oxygen) on the electrical strength to be assessed. Eight molecules show low-energy resonance and a further four have negative R-matrix poles implying that they support an anionic state. Our calculations suggest that molecules with double bonded structures, especially involving C = N, should have the best electrical strength, followed by cyclic and then triple bonded structures. Calculation on the C3F6−n H n (n = 0, 6) series suggest that introducing H atoms in selected positions can decrease GWP while retaining the electrical strength of pure fluorocarbon gases like C3F6.

Symmetry-adapted encodings for qubit number reduction by point-group and other Boolean symmetries

Abstract: A symmetry-adapted fermion-to-spin mapping or encoding that is able to store information about the occupancy of the n spin-orbitals of a molecular system into a lower number of n − k qubits in a quantum computer (where the number of reduced qubits k ranges from 2 to 5 depending on the symmetry of the system) is introduced. This mapping reduces the computational cost of a quantum computing simulation and at the same time enforces symmetry constraints. These symmetry-adapted encodings (SAEs) can be explicitly seen as a block-diagonalization of the Jordan–Wigner qubit Hamiltonian, followed by an orthogonal projection. We provide the form of the Clifford tableau for a general class of fermion-to-qubit encodings, and then use it to construct the map that block-diagonalizes the Hamiltonian in the SAEs. The algorithm proposed does not require any further computations to obtain this map, which is derived directly from the character table of the molecular point group. An implementation of the algorithm is presented as an open-source Python package, QuantumSymmetry, a user guide and code examples. QuantumSymmetry uses open-source quantum chemistry software PySCF for Hartree–Fock calculations, and is compatible with quantum computing toolsets OpenFermion and Qiskit. QuantumSymmetry takes arbitrary user input such as the molecular geometry and atomic basis set to construct the qubit operators that correspond in the appropriate SAE to fermionic operators on the molecular system, such as the second-quantized electronic structure Hamiltonian. QuantumSymmetry is used to produce numerical examples of variational quantum algorithm simulations to find the ground state energy for a number of example molecules, for both Unitary Coupled Clusters with Singles and Doubles and Adaptive Derivative Assembled Pseudo-Trotter Variational Quantum Eigensolver ansätze. We show that, beyond the advantage given by the lower qubit count, the proposed encodings consistently result in shallower and less complex circuits with a reduced number of variational parameters that are able to reach convergence faster and without any loss of computed accuracy.

Cross Sections for Electron Collisions with N2, N2*, and N2+

Abstract: Electron collision cross section data are complied from the literature for electron collisions with the nitrogen molecules, N2, N2+, and N2*. Cross sections are collected and reviewed for total scattering, elastic scattering, momentum transfer, rotational excitation, vibrational excitation, electronic excitation, dissociative processes, and ionization. The literature has been surveyed up to the end of 2021. For each of these processes, the recommended values of the cross sections are presented.

ExoMol line lists – L: High-resolution line lists of H+3, H2D+, D2H+ and D+3.

Abstract: New MiZo line lists are presented for the D2H+ and D$_3^+$ isotopologues of H$_3^+$. These line lists plus the existing H$_3^+$ MiZATeP and the Sochi H2D+ line lists are updated using empirical energy levels generated using the MARVEL procedure for H$_3^+$, H2D+ and D2H+, and effective Hamiltonian energies for D$_3^+$ for which there is significantly less laboratory data available. These updates allow accurate frequencies for far infrared lines for these species to be predicted. Assignments of the energy levels of H$_3^+$ and D$_3^+$ are extended using a combination of high accuracy variational calculations and analysis of transition intensities. All line lists are made available via www.exomol.com.

1 The EChO science case

Abstract: Tinetti, Giovanna; Drossart, Pierre; Eccleston, Paul; Hartogh, Paul; Isaak, Kate; Linder, Martin; Lovis, Christophe; Micela, Giusi; Ollivier, Marc; Puig, Ludovic; Ribas, Ignasi; Snellen, Ignas; Swinyard, Bruce; Allard, France; Barstow, Joanna; Cho, James; Coustenis, Athena; Cockell, Charles; Correia, Alexandre; Decin, Leen; de Kok, Remco; Deroo, Pieter; Encrenaz, Therese; Forget, Francois; Glasse, Alistair; Griffith, Caitlin; Guillot, Tristan; Koskinen, Tommi; Lammer, Helmut; Leconte, Jeremy; Maxted, Pierre; Mueller-Wodarg, Ingo; Nelson, Richard; North, Chris; Pallé, Enric; Pagano, Isabella; Piccioni, Guseppe; Pinfield, David; Selsis, Franck; Sozzetti, Alessandro; Stixrude, Lars; Tennyson, Jonathan; Turrini, Diego; Zapatero-Osorio, Mariarosa; Beaulieu, Jean-Philippe; Grodent, Denis; Guedel, Manuel; Luz, David; Nørgaard-Nielsen, Hans Ulrik; Ray, Tom; Rickman, Hans; Selig, Avri; Swain, Mark; Banaszkiewicz, Marek; Barlow, Mike; Bowles, Neil; Branduardi-Raymont, Graziella; du Foresto, Vincent Coudé; Gerard, Jean-Claude; Gizon, Laurent; Hornstrup, Allan; Jarchow, Christopher; Kerschbaum, Franz; Kovacs, Géza; Lagage, Pierre-Olivier; Lim, Tanya; Lopez-Morales, Mercedes; Malaguti, Giuseppe; Pace, Emanuele; Pascale, Enzo; Vandenbussche, Bart; Wright, Gillian; Zapata, Gonzalo Ramos; Adriani, Alberto; Azzollini, Ruymán; Balado, Ana; Bryson, Ian; Burston, Raymond; Colomé, Josep; Crook, Martin; Di Giorgio, Anna; Griffin, Matt; Hoogeveen, Ruud; Ottensamer, Roland; Irshad, Ranah; Middleton, Kevin; Morgante, Gianluca; Pinsard, Frederic; Rataj, Mirek; Reess, Jean-Michel; Savini, Giorgio; Schrader, Jan-Rutger; Stamper, Richard; Winter, Berend; Abe, L.; Abreu, M.; Achilleos, N.; Ade, P.; Adybekian, V.; Affer, L.; Agnor, C.; Agundez, M.; Alard, C.; Alcala, J.; Allende Prieto, C.; Alonso Floriano, F. J.; Altieri, F.; Alvarez Iglesias, C. A.; Amado, P.; Andersen, A.; Aylward, A.; Baffa, C.; Bakos, G.; Ballerini, P.; and (2015). The EChO science case. Experimental Astronomy, 40(2) pp. 329–391.

ExoMol line lists – XLVIII. High-temperature line list of thioformaldehyde (H2CS)

Abstract: A comprehensive rotation-vibration (ro-vibrational) line list of thioformaldehyde (1H212C32S) that is applicable for elevated temperatures (2000K) is presented. The new MOTY line list covers the 0 to 8000 cm−1 range (wavelengths λ > 1.3μm and contains around 43.5billion transitions between 52.3million states with rotational excitation up to J = 120. Line list calculations utilise a newly determined empirically refined potential energy surface (PES) – the most accurate H2CS PES to date – a previously published high-level ab initio dipole moment surface, and the use of an exact kinetic energy operator for solving the ro-vibrational Schrödinger equation. Post-processing of the MOTY line list is performed by replacing calculated energy levels with empirically-derived values, vastly improving the accuracy of predicted line positions in certain spectral windows and making the line list suitable for high-resolution applications. The MOTY line list is available from the ExoMol database at www.exomol.com and the CDS astronomical database.

Data structures for photoadsorption within the ExoMol project

Abstract: The ExoMol database currently provides comprehensive line lists for modelling the spectroscopic properties of molecules in hot atmospheres. Extending the spectral range of the data provided to ultraviolet (UV) wavelengths brings into play three processes not currently accounted for in the ExoMol data structure, namely photodissociation, which is an important chemical process in its own right, the opacity contribution due to continuum absorption and predissociation which can lead to significant and observable line broadening effects. Data structures are proposed which will allow these processes to be correctly captured and the (strong) temperature-dependent effects predicted for UV molecular photoabsorption in general and photodissociation in particular to be represented.

Optical frequency comb Fourier transform spectroscopy of formaldehyde in the 1250 to 1390 cm$^{-1}$ range: experimental line list and improved MARVEL analysis

Abstract: We use optical frequency comb Fourier transform spectroscopy to record high-resolution, low-pressure, room-temperature spectra of formaldehyde (H$_2$$^{12}$C$^{16}$O) in the range of 1250 to 1390 cm$^{-1}$. Through line-by-line fitting, we retrieve line positions and intensities of 747 rovibrational transitions: 558 from the ${ u}_6$ band, 129 from the ${ u}_4$ band, and 14 from the ${ u}_3$ band, as well as 46 from four different hot bands. We incorporate the accurate and precise line positions (0.4 MHz median uncertainty) into the MARVEL (measured active vibration-rotation energy levels) analysis of the H$_2$CO spectrum. This increases the number of MARVEL-predicted energy levels by 82 and of rovibrational transitions by 5382, and substantially reduces uncertainties of MARVEL-derived H$_2$CO energy levels over a large range: from pure rotational levels below 200 cm$^{-1}$ up to multiply excited vibrational levels at 6000 cm$^{-1}$. This work is an important step toward filling the gaps in formaldehyde data in the HITRAN database.

Measurement and calculation of CO (7-0) overtone line intensities.

Abstract: Intensities of 14 lines in the sixth overtone (7-0) band of carbon monoxide (12C16O) are measured in the visible range between 14 300 and 14 500 cm-1 using a frequency-stabilized cavity ring-down spectrometer. This is the first observation of such a high and weak overtone spectrum of the CO molecule. A theoretical model is constructed and tested based on the use of a high accuracy ab initio dipole moment curve and a semi-empirical potential energy curve. Accurate studies of high overtone transitions provide a challenge to both experiment and theory as the lines are very weak: below 2 × 10-29 cm molecule-1 at 296 K. Agreement between theory and experiment within the experimental uncertainty of a few percent is obtained. However, this agreement is only achieved after issues with the stability of the Davidson correction to the multi-reference configuration interaction calculations are addressed.