arXiv subjects

Sergei N. Yurchenko

Publications and source records attributed to Sergei N. Yurchenko.

At least 55 records · Page 3Linked to original sources

arXiv2022

ExoMol line lists -- XLVII. Rovibronic molecular line list of the calcium monohydroxide radical (CaOH)

Any future detection of the calcium monohydroxide radical (CaOH) in stellar and exoplanetary atmospheres will rely on accurate molecular opacity data. Here, we present the first comprehensive molecular line list of CaOH covering the \A--\X\ rotation-vibration-electronic and \X--\X\ rotation-vibration bands. The newly computed OYT6 line list contains over 24.2 billion transitions between 3.2 million energy levels with rotational excitation up to $J=175.5$. It is applicable to temperatures up to $T=3000$~K and covers the 0\,--\,35\,000~cm$^{-1}$ range (wavelengths $λ> 0.29$~$μ$m) for rotational, rotation-vibration and the \A--\X\ electronic transition. The strong band around 16\,000~cm$^{-1}$ ($λ= 0.63$~$μ$m) is likely to be of interest in future astronomical observations, particularly in hot rocky exoplanets where temperatures can become extremely high. The OYT6 line list has been generated using empirically-refined \X\ and \A\ state potential energy surfaces, high-level \textit{ab initio} transition dipole moment surfaces and a rigorous treatment of both Renner-Teller and spin-orbit coupling effects, which are necessary for correctly modelling the CaOH spectrum. Post-processing of the CaOH line list has been performed so as to tailor it to high-resolution applications, i.e.\ by replacing calculated energy levels with more accurate empirically-derived values (where available), hence improving the accuracy of the predicted line positions in certain regions. The OYT6 line list is available from the ExoMol database at http://www.exomol.com and the CDS astronomical database.

astro-ph.EP↗

arXiv2022

ExoMol line lists -- XLV. Rovibronic molecular line lists of calcium monohydride (CaH) and magnesium monohydride (MgH)

New molecular line lists for calcium monohydride ($^{40}$Ca$^{1}$H) and magnesium monohydride ($^{24}$Mg$^{1}$H) and its minor isotopologues ($^{25}$Mg$^{1}$H and $^{26}$Mg$^{1}$H) are presented. The rotation-vibration-electronic (rovibronic) line lists, named \texttt{XAB}, consider transitions involving the \X, \A, and \BBp\ electronic states in the 0--30\,000~cm$^{-1}$ region (wavelengths $λ> 0.33$~$μ$m) and are suitable for temperatures up to 5000 K. A comprehensive analysis of the published spectroscopic literature on CaH and MgH is used to obtain new extensive datasets of accurate rovibronic energy levels with measurement uncertainties and consistent quantum number labelling. These datasets are used to produce new spectroscopic models for CaH and MgH, composed of newly empirically-refined potential energy curves and couplings in/between the different electronic states (e.g.\ spin-orbit, electronic angular momentum, Born-Oppenheimer breakdown, spin-rotation, $Λ$-doubling) and previously published \textit{ab initio} transition dipole moment curves. Along with Einstein $A$ coefficients, state lifetimes and Landé $g$-factors are provided, the latter being particularly useful as CaH and MgH can be used to probe stellar magnetic fields. Computed energy levels have been replaced with the more accurate empirical values (if available) when post-processing the line lists, thus tailoring the line lists to high resolution applications. The \texttt{XAB} line lists are available from the ExoMol database at http://www.exomol.com and the CDS astronomical database.

astro-ph.EP↗

arXiv2022

AlH lines in the blue spectrum of Proxima Centauri

The recently-computed ExoMol line lists for isotopologues of AlH are used to analyse the blue spectrum (4000-4500 Å) of Proxima Cen (M5.5 V). Comparison of the observed and computed spectra enables the identification of a large number of 27AlH lines of the A1Π - X1Σ+ band system: the spectral range covering 1-0, 0-0 and 1-1 bands is dominated by clearly resolved AlH lines. We reveal the diffuse nature of transitions close to the dissociation limit which appears in the form of increasingly wider(up to 5 Å) and shallower (up to the continuum confusion limit) AlH line profiles. The predicted wavelengths of AlH diffuse lines are systematically displaced. The effect broadening by pre-dissociation states on the line profiles is included by increasing the radiative damping rate by up to 5 orders of magnitude. We determine empirical values of damping rates for a number of the clean 0-0 Q-branch transitions by comparing the observed and synthetic stellar spectra. We find excellent agreement between our damping rates and lifetimes available in the literature. A comparison of 27Al1H ExoMol and REALH spectra shows that the observed spectrum is better described by the ExoMol line list. A search for 26Al1H lines in the Proxima Cen spectrum does not reveal any notable features; giving an upper limit of 27Al1H/26Al1H {>} 100.

astro-ph.SR↗

arXiv2022

ExoMol photodissociation cross sections I: HCl and HF

Photon initiated chemistry, \textit{i.e.} the interaction of light with chemical species, is a key factor in the evolution of the atmosphere of exoplanets. For planets orbiting stars in UV-rich environments, photodissociation induced by high energy photons dominates the atmosphere composition and dynamics. The rate of photodissociation can be highly dependent on atmospheric temperature, as increased temperature leads to increased population of vibrational excited states and the consequent lowering of the photodissociation threshold. This paper inaugurates a new series of papers presenting computed temperature-dependent photodissociation cross sections with rates generated for different stellar fields. Cross sections calculations are performed by solving the time-independent Schrödinger equation for each electronic state involved in the process. Here photodissociation cross sections for hydrogen chloride and hydrogen fluoride are computed for a grid of 34 temperatures between 0 and 10~000 K. Use of different radiation fields shows that for the Sun and cooler stars the photodissociation rate can increase exponentially for molecular temperatures above 1000 K; conversely the photodissociation rates in UV rich fields instead are almost insensitive to the temperature of the molecule. Furthermore, these rates show extreme sensitivity to the radiation model used for cool stars, suggesting that further work on these may be required. The provision of an ExoMol database of cross sections is discussed.

physics.chem-ph↗

arXiv2022

Cross-sections for heavy atmospheres: H$_2$O continuum

Most of the exoplanets detected up to now transit in front of their host stars, allowing for the generation of transmission spectra; the study of exoplanet atmospheres relies heavily upon accurate analysis of these spectra. Recent discoveries mean that the study of atmospheric signals from low-mass, temperate worlds are becoming increasingly common. The observed transit depth in these planets is small and more difficult to analyze. Analysis of simulated transmission spectra for two small, temperate planets (GJ 1214 b and K2-18 b) is presented, giving evidence for significant differences in simulated transit depth when the water vapor continuum is accounted for when compared to models omitting it. These models use cross-sections from the CAVIAR lab experiment for the water self-continuum up to 10,000 cm$^{-1}$; these cross-sections exhibit an inverse relationship with temperature, hence lower-temperature atmospheres are the most significantly impacted. Including the water continuum strongly affects transit depths, increasing values by up to 80 ppm, with the differences for both planets being detectable with the future space missions Ariel and JWST. It is imperative that models of exoplanet spectra move toward adaptive cross-sections, increasingly optimized for H$_2$O-rich atmospheres. This necessitates including absorption contribution from the water vapor continuum into atmospheric simulations.

astro-ph.EP↗

arXiv2022

Cross-sections for heavy atmospheres: H$_2$O self-broadening

The discovery of super-Earth and mini-Neptune exoplanets means that atmospheric signals from low-mass, temperate exoplanets are being increasingly studied. The signal acquired as the planet transits its host star, known as the transit depth, is smaller for these planets and, as such, more difficult to analyze. The launch of the space telescopes James Webb (JWST) & Ariel will give rise to an explosion in the quality and quantity of spectroscopic data available for an unprecedented number of exoplanets in our galaxy. Accurately extracting the information content, thereby permitting atmospheric science, of such data-sets will require robust models and techniques. We present here the analysis of simulated transmission spectra for water-rich atmospheres, giving evidence for non-negligible differences in simulated transit depths when self-broadening of H$_2$O is correctly accounted for, compared with the currently typically accepted standard of using H$_2$ and He-broadened cross-sections. Our case-study analysis is carried out on two super-Earths, focusing on water-based atmospheres, ranging from H$_2$-rich to H$_2$O-rich. The transit depth is considerably affected, increasing values by up to 60 ppm, which is shown to be detectable with JWST and Ariel. The differences are most pronounced for the lighter (i.e. $mu$ $\sim$ 4) atmospheres. Our work illustrates that it is imperative that the field of exoplanet spectroscopy moves toward adapted cross-sections, increasingly optimized for high-mu atmospheres for studies of super-Earths and mini-Neptunes.

astro-ph.EP↗

arXiv2022

Non-Local thermal equilibrium spectra of atmospheric molecules for exoplanets

Here we present a study of non-LTE effects on the exoplanetary spectra of a collection of molecules which are key in the investigation of exoplanet atmospheres: water, methane, carbon monoxide and titanium oxide. These molecules are chosen as examples of different spectral ranges (IR and UV), molecular types (diatomics and polyatomics) and spectral types (electronic and ro-vibrational); the importance of different vibrational bands in forming distinct non-LTE spectral features are investigated. Most notably, such key spectral signatures for distinguishing between the LTE and non-LTE cases include: for CH4 the 3.15 $μ$m band region; for H2O the 2.0 $μ$m and 2.7 $μ$m band regions; for TiO, a strong variation in intensity in the bands between 0.5 and 0.75 $μ$m; and a sole CO signature between 5 and 6 $μ$m. The analysis is based on the ExoMol cross sections and takes advantage of the extensive vibrational assignment of these molecular line lists in the ExoMol database. We examine LTE and non-LTE cross sections under conditions consistent with those on WASP-12b and WASP-76b using the empirically motivated bi-temperature Treanor model. In addition, we make a simplistic forward model simulation of transmission spectra for H2O in the atmosphere of WASP-12b using the TauREx 3 atmospheric modelling code.

astro-ph.EP↗

arXiv2022

A method for the variational calculation of hyperfine-resolved rovibronic spectra of diatomic molecules

An algorithm for the calculation of hyperfine structure and spectra of diatomic molecules based on the variational nuclear motion is presented. Hyperfine coupling terms considered are Fermi-contact, nuclear spin-electron spin dipole-dipole, nuclear spin-orbit, nuclear spin-rotation and nuclear electric quadrupole interactions. Initial hyperfine-unresolved wavefunctions are obtained for given set of potential energy curves and associated couplings by variation solution of the nuclear-motion Schrödinger equation. Fully hyperfine-resolved parity-conserved rovibronic Hamiltonian matrices for a given final angular momentum, $\bm{F}$, are constructed and then diagonalized to give hyperfine-resolved energies and wavefunctions.Electric transition dipole moment curves can then be used to generate a hyperfine-resolved line list by applying rigorous selection rules.The algorithm is implemented in \textsc{Duo}, which is a general program for calculating spectra of diatomic molecules. This approach is tested for NO and MgH,and the results are compared to experiment and shown to be consistent with those given the well-used effective Hamiltonian code PGOPHER.

physics.chem-ph↗

arXiv2021

ExoMol line lists -- XLIV. IR and UV line list for silicon monoxide (SiO)

A new silicon monoxide ($^{28}$Si$^{16}$O) line list covering infrared, visible and ultraviolet regions called SiOUVenIR is presented. This line list extends the infrared EBJT ExoMol line list by including vibronic transitions to the $A\,{}^{1}Π$ and $E\,{}^{1}Σ^{+}$ electronic states. Strong perturbations to the $A\,{}^{1}Π$ band system are accurately modelled through the treatment of 6 dark electronic states: $C\,{}^{1}Σ^{-}$, $D\,{}^{1}Δ$, $a\,{}^{3}Σ^{+}$, $b\,{}^{3}Π$, $e\,{}^{3}Σ^{-}$ and $d\,{}^{3}Δ$. Along with the $X\,{}^{1}Σ^{+}$ ground state, these 9 electronic states were used to build a comprehensive spectroscopic model of SiO using a combination of empirical and ab initio curves, including the potential energy (PE), spin-orbit (SO), electronic angular momentum (EAM) and (transition) dipole moment curves. The ab initio PE and coupling curves, computed at the multireference configuration interaction (MRCI) level of theory, were refined by fitting their analytical representations to 2617 experimentally derived SiO energy levels determined from 97 vibronic bands belonging to the $X$-$X$, $E$-$X$ and $A$-$X$ electronic systems through the MARVEL procedure. 112 observed forbidden transitions from the $C$-$X$, $D$-$X$, $e$-$X$, and $d$-$X$ bands were assigned using our predictions, and these could be fed back into the MARVEL procedure. The SiOUVenIR line list was computed using published ab initio transition dipole moments for the $E$-$X$ and $A$-$X$ bands; the line list is suitable for temperatures up to 10,000 K and for wavelengths longer than 140 nm. SiOUVenIR is available from www.exomol.com and the CDS database.

astro-ph.EP↗

arXiv2021

Rovibronic spectroscopy of PN from first principles

We report an ab initio study on the rovibronic spectroscopy of the closed-shell diatomic molecule phosphorous mononitride, PN. The study considers the nine lowest electronic states, $X\,{}^{1}Σ^{+}$, $A\,{}^{1}Π$, $C\,{}^{1}Σ^{-}$, $D\,{}^{1}Δ$, $E\,{}^{1}Σ^{-}$, $a\,{}^{3}Σ^{+}$, $b\,{}^{3}Π$, $d\,{}^{3}Δ$ and $e\,{}^{3}Σ^{-}$ using high level electronic structure theory and accurate nuclear motion calculations. The ab initio data cover 9 potential energy, 14 spin-orbit coupling, 7 electronic angular momentum coupling, 9 electric dipole moment and 8 transition dipole moment curves. The Duo nuclear motion program is used to solve the coupled nuclear motion Schrödinger equations for these nine electronic states and to simulate rovibronic absorption spectra of $^{31}$P$^{14}$N for different temperatures, which are compared to available spectroscopic studies. Lifetimes for all states are calculated and compared to previous results from the literature. The calculated lifetime of the $A\,{}^{1}Π$ state shows good agreement with an experimental value from the literature, which is an important quality indicator for the ab initio $A$-$X$ transition dipole moment.

physics.atom-ph↗

arXiv2021

A high-resolution line list for AlO

Indications of aluminium monoxide in atmospheres of exoplanets are being reported. Studies using high-resolution spectroscopy should allow a strong detection but require high accuracy laboratory data. A \textsc{marvel} (measured active rotational-vibrational energy levels) analysis is performed for the available spectroscopic data on $^{27}$Al$^{16}$O: 22\,473 validated transitions are used to determine 6\,485 distinct energy levels. These empirical energy levels are used to provide an improved, spectroscopically accurate version of the ExoMol ATP line list for $^{27}$Al$^{16}$O; at the same time the accuracy of the line lists for the isotopically-substituted species $^{26}$Al$^{16}$O, $^{27}$Al$^{17}$O and $^{27}$Al$^{18}$O are improved by correcting levels in line with the corrections used for $^{27}$Al$^{16}$O. These line lists are available from the ExoMol database at http://www.exomol.com.

astro-ph.EP↗

arXiv2021

A spectroscopic model for the low-lying electronic states of NO

The rovibronic structure of A$^2Σ^+$, B$^2Π$ and C$^2Π$ states of nitric oxide (NO)is studied with the aim of producing comprehensive line lists for its near ultraviolet spectrum. Empirical energy levels for the three electronic states are determined using the a combination of the empirical MARVEL procedure and ab initio calculations, and the available experimental data are critically evaluated. Abinito methods which deal simultaneously with the Rydberg-like A$^2Σ^+$ and C$^2Π$, and the valence B$^2Π$ state are tested. Methods of modeling the sharp avoided crossing between the B$^2Π$ and C$^2Π$ states are tested. A rovibronic Hamiltonian matrix is constructed using variational nuclear motion program DUO whose eigenvalues are fitted to the MARVEL energy levels. The matrix also includes coupling terms obtained from the refinement of the ab initio potential energy and spin-orbit coupling curves. Calculated and observed energy levels agree well with each other, validating the applicability of our method and providing a useful model for this open shell system.

physics.chem-ph↗

arXiv2021

ExoMol molecular line lists -- XLII: Rovibronic molecular line list for the low-lying states of NO

An accurate line list, called XABC, is computed for nitric oxide which covers its pure rotational, vibrational and rovibronic spectra. A mixture of empirical and theoretical electronic transition dipole moments are used for the final calculation of $^{14}\mathrm{N}^{16}\mathrm{O}$ rovibronic $\mathrm{A}\,^2Σ^+$ -- $\mathrm{X}\,^2Π$, $\mathrm{B}\,^2Π$ -- $\mathrm{X}^2Π$ and $\mathrm{C}\,^2Π$ -- $\mathrm{X}\,^2Π$ which correspond to the $γ$, $β$ and $δ$ band systems, respectively, as well as minor improvements to transitions within the $\mathrm{X}\,^2Π$ ground state. The work is a major update of the ExoMol NOname line list. It provides a high-accuracy NO ultraviolet line list covering the complicated regions where the $\mathrm{B}\,^2Π$-$\mathrm{C}\,^2Π$ states interact. XABC provides comprehensive data for the lowest four doublet states of NO in the region of $λ> 160 ~ \mathrm{nm}$ ($\tildeν < 63~000~\mathrm{cm}^{-1}$) for the analysis of atmospheric NO on Earth, Venus or Mars, other astronomical observations and applications. The data is available via www.exomol.com.

astro-ph.EP↗

arXiv2021

Theoretical rovibronic spectroscopy of the calcium monohydroxide radical (CaOH)

The rovibronic (rotation-vibration-electronic) spectrum of the calcium monohydroxide radical (CaOH) is of interest to studies of exoplanet atmospheres and ultracold molecules. Here, we theoretically investigate the $\tilde{A}\,^2Π$--$\tilde{X}\,^2Σ^+$ band system of CaOH using high-level \textit{ab initio} theory and variational nuclear motion calculations. New potential energy surfaces (PESs) are constructed for the $\tilde{X}\,^2Σ^+$ and $\tilde{A}\,^2Π$ electronic states along with $\tilde{A}$--$\tilde{X}$ transition dipole moment surfaces (DMSs). For the ground $\tilde{X}\,^2Σ^+$ state, a published high-level \textit{ab initio} PES is empirically refined to all available experimental rovibrational energy levels up to $J=15.5$, reproducing the observed term values with a root-mean-square (rms) error of 0.06~cm$^{-1}$. Large-scale multireference configuration interaction (MRCI) calculations using quintuple-zeta quality basis sets are employed to generate the $\tilde{A}\,^2Π$ state PESs and $\tilde{A}$--$\tilde{X}$ DMSs. Variational calculations consider both Renner-Teller and spin-orbit coupling effects, which are essential for a correct description of the spectrum of CaOH. Computed rovibronic energy levels of the $\tilde{A}\,^2Π$ state, line list calculations up to $J=125.5$, and an analysis of Renner-Teller splittings in the $ν_2$ bending mode of CaOH are discussed.

physics.chem-ph↗

arXiv2021

Electric quadrupole transitions in carbon dioxide

Recent advances in the high sensitivity spectroscopy have made it possible, in combination with accurate theoretical predictions, to observe for the first time very weak electric quadrupole transitions in a polar polyatomic molecule of water. Here we present accurate theoretical predictions of the complete quadrupole ro-vibrational spectrum of a non-polar molecule CO$_2$, important in atmospheric and astrophysical applications. Our predictions are validated by recent cavity enhanced absorption spectroscopy measurements and are used to assign few weak features in the recent ExoMars ACS MIR spectroscopic observations of the martian atmosphere. Predicted quadrupole transitions appear in some of the mid-infrared CO$_2$ and water vapor transparency regions, making them important for detection and characterization of the minor absorbers in water- and CO$_2$-rich environments, such as present in the atmospheres of Earth, Venus and Mars.

physics.atom-ph↗

arXiv2021

Modelling the non-local thermodynamic equilibrium spectra of silylene (SiH2)

This paper sets out a robust methodology for modelling spectra of polyatomic molecules produced in reactive or dissociative environments, with vibrational populations outside local thermal equilibrium (LTE). The methodology is based on accurate, extensive ro-vibrational line lists containing transitions with high vibrational excitations and relies on the detailed ro-vibrational assignments. The developed methodology is applied to model non-LTE IR and visible spectra of silylene (SiH$_2$) produced in a decomposition of disilane (Si$_2$H$_6$), a reaction of technological importance. Two approaches for non-LTE vibrational populations of the product SiH$_2$ are introduced: a simplistic 1D approach based on the Harmonic approximation and a full 3D model incorporating accurate vibrational wavefunctions of SiH$_2$ computed variationally with the TROVE (Theoretical ROVibrational Energy) program. We show how their non-LTE spectral signatures can be used to trace different reaction channels of molecular dissociations.

physics.chem-ph↗

arXiv2021

Five carbon- and nitrogen-bearing species in a hot giant planet's atmosphere

The atmospheres of gaseous giant exoplanets orbiting close to their parent stars (hot Jupiters) have been probed for nearly two decades. They allow us to investigate the chemical and physical properties of planetary atmospheres under extreme irradiation conditions. Previous observations of hot Jupiters as they transit in front of their host stars have revealed the frequent presence of water vapour and carbon monoxide in their atmospheres; this has been studied in terms of scaled solar composition under the usual assumption of chemical equilibrium. Both molecules as well as hydrogen cyanide were found in the atmosphere of HD 209458b, a well studied hot Jupiter (with equilibrium temperature around 1,500 kelvin), whereas ammonia was tentatively detected there and subsequently refuted. Here we report observations of HD 209458b that indicate the presence of water (H2O), carbon monoxide (CO), hydrogen cyanide (HCN), methane (CH4), ammonia (NH3) and acetylene (C2H2), with statistical significance of 5.3 to 9.9 standard deviations per molecule. Atmospheric models in radiative and chemical equilibrium that account for the detected species indicate a carbon-rich chemistry with a carbon-to-oxygen ratio close to or greater than 1, higher than the solar value (0.55). According to existing models relating the atmospheric chemistry to planet formation and migration scenarios, this would suggest that HD 209458b formed far from its present location and subsequently migrated inwards. Other hot Jupiters may also show a richer chemistry than has been previously found, which would bring into question the frequently made assumption that they have solar-like and oxygen-rich compositions.

astro-ph.EP↗

arXiv2021

An improved rovibrational linelist of formaldehyde, \spec{h212c16o}

Published high-resolution rotation-vibration transitions of \spec{h212c16o}, the principal isotopologue of methanal, are analyzed using the MARVEL (Measured Active Rotation-Vibration Energy Levels) procedure. The literature results are augmented by new, high-accuracy measurements of pure rotational transitions within the ground, $ν_3$, $ν_4$, and $ν_6$ vibrational states. Of the \nbNonRedTr\ non-redundant transitions processed, which come from \nbSr\ sources including the present work, \nbValTr\ could be validated, providing \nbEl\ empirical energy levels of \spec{h212c16o}\ with statistically well-defined uncertainties. All the empirical rotational-vibrational energy levels determined are used to improve the accuracy of ExoMol's AYTY line list for hot formaldehyde. The complete list of collated experimental transitions, the empirical energy levels determined, as well as the extended and improved line list are provided as Supplementary Material.

astro-ph.SR↗