arXiv subjects

Laura K. McKemmish

Publications and source records attributed to Laura K. McKemmish.

36 records · Page 2Linked to original sources

arXiv2020

Analysis of the TiO isotopologues in stellar optical spectra

This study is based on the use of the new ExoMol TiO rovibronic line lists to identify and model TiO isotopologue features in spectra of M-dwarfs. We aim to investigate problems involving the computation of electronic bands for different isotopologues of TiO by modelling optical spectra of late-type stars and to determine their Ti isotopic abundances, to compare the TiO isotopologues spectra computed using line lists by different authors. We fit theoretical synthetic spectra to the observed stellar molecular bands of TiO. We model spectra of two M-dwarfs: GJ 15A (M1V) and GJ 15B (M3 V) to determine Ti isotopic ratios in their atmospheres. We demonstrate the accuracy of the ExoMol {\sc Toto} line list for differentisotopologues of TiO and the possibility of determining accurate Ti isotope abundances in a numberof spectral ranges. The 7580--7594 Å spectral range seems particularly useful, with two atomic linesof Fe I and molecular band heads of $^{50}Ti$O, $^{49}Ti$O, $^{48}Ti$O, $^{47}Ti$O clearly observable in our two M-dwarf spectra. We determine non-solar Ti isotopic ratios of $^{46}Ti$ : $^{47}Ti$ : $^{48}Ti$ : $^{49}Ti$ : $^{50}Ti$ = 7.9 : 5.2 : 72.8 : 7.9 :6.2 for GJ 15A and 7.4 : 4.2 : 76.6 : 5.8 : 6.0 for GJ 15B with accuracy of order $\pm$ 0.2. [Ti] = 0.040 and 0.199 within accuracy $\pm$ 0.10 were also determined for GJ 15A and GJ 15B, respectively. We find that the ExoMol {\sc Toto} TiO line list: a) describes the fine details in line position and intensities of the M-dwarf spectra better than other available TiO line lists; b) correctly reproduces the positions and intensities of the TiO isotopologue band heads observed in M-dwarf spectra; c) can be used to determine Ti isotope abundances in atmospheres of M-stars.

astro-ph.SR↗

arXiv2020

The 2020 release of the ExoMol database: molecular line lists for exoplanet and other hot atmospheres

The ExoMol database (www.exomol.com) provides molecular data for spectroscopic studies of hot atmospheres. While the data is intended for studies of exoplanets and other astronomical bodies, the dataset is widely applicable. The basic form of the database is extensive line lists; these are supplemented with partition functions, state lifetimes, cooling functions, Landé g-factors, temperature-dependent cross sections, opacities, pressure broadening parameters, $k$-coefficients and dipoles. This paper presents the latest release of the database which has been expanded to consider 80 molecules and 190 isotopologues totaling over 700 billion transitions. While the spectroscopic data is concentrated at infrared and visible wavelengths, ultraviolet transitions are being increasingly considered in response to requests from observers. The core of the database comes from the ExoMol project which primarily uses theoretical methods, albeit usually fine-tuned to reproduce laboratory spectra, to generate very extensive line lists for studies of hot bodies. The data has recently been supplemented by line lists deriving from direct laboratory observations, albeit usually with the use of ab initio transition intensities. A major push in the new release is towards accurate characterisation of transition frequencies for use in high resolution studies of exoplanets and other bodies.

astro-ph.SR↗

arXiv2020

Assessing Spectra and Thermal Inversions due to TiO in Hot Jupiter Atmospheres

Recent detections of thermal inversions in the dayside atmospheres of some hot Jupiters are motivating new avenues to understand the interplay between their temperature structures and other atmospheric conditions. In particular, TiO has long been proposed to cause thermal inversions in hot Jupiters, depending on other factors such as stellar irradiation, C/O, and vertical mixing. TiO also has spectral features in the optical and near-infrared that have been detected. However, interpretations of TiO signatures rely on the accuracy of TiO opacity used in the models. The recently reported Toto TiO line list provides a new opportunity to investigate these dependencies, which is the goal of the present work. First, we investigate how the Toto line list affects observable transmission and emission spectra of hot Jupiters at low and high resolution. The improvement in the Toto line list compared to a previous line list results in observable differences in the model spectra, particularly in the optical at high resolution. Secondly, we explore the interplay between temperature structure, irradiation and composition with TiO as the primary source of optical opacity, using 1D self-consistent atmospheric models. Among other trends, we find that the propensity for thermal inversions due to TiO peaks at C/O$\sim$0.9, consistent with recent studies. Using these models, we further assess metrics to quantify thermal inversions due to TiO, compared to frequently-used Spitzer photometry, over a range in C/O, irradiation, metallicity, gravity and stellar type.

astro-ph.EP↗

arXiv2020

Mixed ramp-Gaussian basis sets for core-dependent properties: STO-RG and STO-R2G for Li-Ne

The traditional Gaussian basis sets used in modern quantum chemistry lack an electron-nuclear cusp, and hence struggle to accurately describe core electron properties. A recently introduced novel type of basis set, mixed ramp-Gaussians, introduce a new primitive function called a ramp function which addresses this issue. This paper introduces three new mixed ramp-Gaussian basis sets - STO-R, STO-RG and STO-R2G, made from a linear combination of ramp and Gaussian primitive functions - which are derived from the single-core-zeta Slater basis sets for the elements Li to Ne. This derivation is done in an analogous fashion to the famous STO-$n$G basis sets. The STO-RG basis functions are found to outperform the STO-3G basis functions and STO-R2G outperforms STO-6G, both in terms of wavefunction fit and other key quantities such as the one-electron energy and the electron-nuclear cusp. The second part of this paper performs preparatory investigations into how standard all-Gaussian basis sets can be converted to ramp-Gaussian basis sets through modifying the core basis functions. Using a test case of the 6-31G basis set for carbon, we determined that the second Gaussian primitive is less important when fitting a ramp-Gaussian core basis function directly to an all-Gaussian core basis function than when fitting to a Slater basis function. Further, we identified the basis sets that are single-core-zeta and thus should be most straightforward to convert to mixed ramp-Gaussian basis sets in the future.

physics.chem-ph↗

arXiv2020

Non-detection of TiO and VO in the atmosphere of WASP-121b using high-resolution spectroscopy

Thermal inversions have long been predicted to exist in the atmospheres of ultra-hot Jupiters. However, detection of two species thought to be responsible -- TiO and VO -- remain elusive. We present a search for TiO and VO in the atmosphere of the ultra-hot Jupiter WASP-121b ($T_\textrm{eq} \gtrsim 2400$ K), an exoplanet already known to show water features in its dayside spectrum characteristic of a temperature inversion as well as tentative evidence for VO at low-resolution. We observed its transmission spectrum with UVES/VLT and used the cross-correlation method -- a powerful tool for the unambiguous identification of the presence of atomic and molecular species -- in an effort to detect whether TiO or VO were responsible for the observed temperature inversion. No evidence for the presence of TiO or VO was found at the terminator of WASP-121b. By injecting signals into our data at varying abundance levels, we set rough detection limits of $[\text{VO}] \lesssim -7.9$ and $[\text{TiO}] \lesssim -9.3$. However, these detection limits are largely degenerate with scattering properties and the position of the cloud deck. Our results may suggest that neither TiO or VO are the main drivers of the thermal inversion in WASP-121b, but until a more accurate line list is developed for VO, we cannot conclusively rule out its presence. Future work will search for finding other strong optically-absorbing species that may be responsible for the excess absorption in the red-optical.

astro-ph.EP↗

arXiv2019

ExoMol Molecular linelists -- XXXIII. The spectrum of Titanium Oxide

Accurate line lists are crucial for correctly modelling a variety of astrophysical phenomena, including stellar photospheres and the atmospheres of extra-solar planets. This paper presents a new line database Toto for the main isotopologues of titanium oxide (TiO): $^{46}$Ti$^{16}$O, $^{47}$Ti$^{16}$O, $^{48}$Ti$^{16}$O, $^{49}$Ti$^{16}$O and $^{50}$Ti$^{16}$O. The TiO line list contains transitions with wave-numbers up to 30,000 cm$^{-1}$ ie long-wards of 0.33 $μ$m. The Toto line list includes all dipole-allowed transitions between 13 low-lying electronic states (X $^3Δ$, a $^1Δ$, d $^1Σ^+$, E $^3Π$, A $^3Φ$ B $^3Π$, C $^3Δ$, b $^1Π$, c $^1Φ$, f $^1Δ$, e $^1Σ^+$). Ab initio potential energy curves (PECs) are computed at the icMRCI level and combined with spin-orbit and other coupling curves. These PECs and couplings are iteratively refined to match known empirical energy levels. Accurate line intensities are generated using ab initio dipole moment curves. The Toto line lists are appropriate for temperatures below 5000 K and contain 30 million transitions for TiO; it is made available in electronic form via the CDS data centre and via www.exomol.com. Tests of the line lists show greatly improved agreement with observed spectra for objects such as M-dwarfs GJ876 and GL581.

astro-ph.SR↗

arXiv2019

Low temperature scattering with the R-matrix method: argon-argon scattering

Results for elastic atom-atom scattering are obtained as a first practical application of RmatReact, a new code for generating high-accuracy scattering observables from potential energy curves. RmatReact has been created in response to new experimental methods which have paved the way for the routine production of ultracold atoms and molecules, and hence the experimental study of chemical reactions involving only a small number of partial waves. Elastic scattering between argon atoms is studied here. There is an unresolved discrepancy between different argon-argon potential energy curves which give different numbers of vibrational bound states and different scattering lengths for the argon-argon dimer. Depending on the number of bound states, the scattering length is either large and positive or large and negative. Scattering observables, specifically the scattering length, effective range, and partial and total cross-sections, are computed at low collision energies and compared to previous results. In general, good agreement is obtained, although our full scattering treatment yields resonances which are slightly lower in energy and narrower than previous determinations using the same potential energy curve.

physics.chem-ph↗

arXiv2019

General Mathematical Formulation of Scattering Processes in Atom-Diatomic Collisions in the RmatReact Methodology

Accurately modelling cold and ultracold reactive collisions occuring over deep potential wells, such as \ce{D+ + H2 -> H+ + HD}, requires the development of new theoretical and computational methodologies. One potentially useful framework is the R-matrix method adopted widely for electron-molecule collisions which has more recently been applied to non-reactive heavy particle collisions such as Ar-Ar. The existing treatment of non-reactive elastic and inelastic scattering needs to be substantially extended to enable modelling of reactive collisions: this is the subject of this paper. Herein, we develop the general mathematical formulation for non-reactive elastic and inelastic scattering, photo-association, photo-dissociation, charge exchange and reactive scattering using the R-matrix method. Of particular note is that the inner region, of central importance to calculable R-matrix methodologies, must be finite in all scattering coordinates rather than a single scattering coordinate as for non-reactive scattering. % The choice of coordinate set and basis function is these cases becomes more complexThis introduces substantial challenges to the basis sets utilised in practical calculations as integrals over finite domains are often much more challenging than over infinite domains for this problem.

physics.chem-ph↗

arXiv2018

A global potential energy surface for H$_3^+$

A globally correct potential energy surface (PES) for the \hp\ molecular ion is presented. The Born-Oppenheimer (BO) \ai\ grid points of Pavanello et. al. [\textit{J. Chem. Phys.} {\bf 136}, 184303 (2012)] are refitted as BOPES75K, which reproduces the energies below dissociation with a root mean square deviation of 0.05~\cm; points between dissociation and 75\,000 \cm\ are reproduced with the average accuracy of a few wavenumbers. The new PES75K+ potential combines BOPES75K with adiabatic, relativistic and quantum electrodynamics (QED) surfaces to provide the most accurate representation of the \hp\ global potential to date, overcoming the limitations on previous high accuracy H$_3^+$ PESs near and above dissociation. PES75K+ can be used to provide predictions of bound rovibrational energy levels with an accuracy of approaching 0.1~\cm. Calculation of rovibrational energy levels within PES75K+ suggests that the non-adiabatic correction remains a limiting factor. The PES is also constructed to give the correct asymptotic limit making it suitable for use in studies of the H$^+$\,+\,H$_2$ prototypical chemical reaction. An improved dissociation energy for H$_3^+$ is derived as $D_0\,=\,$35\,076\,$\pm\,2\,$cm$^{-1}$.

physics.chem-ph↗

arXiv2018

Low temperature scattering with the R-matrix method: the Morse potential

Experiments are starting to probe collisions and chemical reactions between atoms and molecules at ultra-low temperatures. We have developed a new theoretical procedure for studying these collisions using the R-matrix method. Here this method is tested for the atom -- atom collisions described by a Morse potential. Analytic solutions for continuum states of the Morse potential are derived and compared with numerical results computed using an R-matrix method where the inner region wavefunctions are obtained using a standard nuclear motion algorithm. Results are given for eigenphases and scattering lengths. Excellent agreement is obtained in all cases. Progress in developing a general procedure for treating ultra-low energy reactive and non-reactive collisions is discussed.

physics.chem-ph↗

arXiv2018

The ExoMol database: molecular line lists for exoplanet and other hot atmospheres

The ExoMol database (www.exomol.com) provides extensive line lists of molecular transitions which are valid over extended temperatures ranges. The status of the current release of the database is reviewed and a new data structure is specified. This structure augments the provision of energy levels (and hence transition frequencies) and Einstein $A$ coefficients with other key properties, including lifetimes of individual states, temperature-dependent cooling functions, Landé $g$-factors, partition functions, cross sections, $k$-coefficients and transition dipoles with phase relations. Particular attention is paid to the treatment of pressure broadening parameters. The new data structure includes a definition file which provides the necessary information for utilities accessing ExoMol through its application programming interface (API). Prospects for the inclusion of new species into the database are discussed.

astro-ph.GA↗

arXiv2018

ExoMol molecular line lists - XXVI: spectra of SH and NS

Line lists for the sulphur-containing molecules SH (the mercapto radical) and NS are computed as part of the ExoMol project. These line lists consider transitions within the $X$ ${}^2Π$ ground state for $^{32}$SH, $^{33}$SH, $^{34}$SH and $^{\text{32}}$SD, and $^{14}$N$^{32}$S, $^{14}$N$^{33}$S, $^{14}$N$^{34}$S, $^{14}$N$^{36}$S and $^{15}$N$^{32}$S. Ab initio potential energy (PEC) and spin-orbit coupling (SOC) curves are computed and then improved by fitting to experimentally observed transitions. Fully ab initio dipole moment curves (DMCs) computed at high level of theory are used to produce the final line lists. For SH, our fit gives a root-mean-square (rms) error of 0.03 cm$^{-1}$ between the observed ($v_{\rm max}=4$, $J_{\rm max} = 34.5$) and calculated transitions wavenumbers; this is extrapolated such that all $X$ $^2Π$ rotational-vibrational-electronic (rovibronic) bound states are considered. For $^{\text{32}}$SH the resulting line list contains about 81000 transitions and 2300 rovibronic states, considering levels up to $v_{\rm max} = 14$ and $J_{\rm max} = 60.5$. For NS the refinement used a combination of experimentally determined frequencies and energy levels and led to an rms fitting error of 0.002 cm$^{-1}$. Each NS calculated line list includes around 2.8 million transitions and 31000 rovibronic states with a vibrational range up to $v=53$ and rotational range to $J=235.5$, which covers up to 23000 cm$^{-1}$. Both line lists should be complete for temperatures up to 5000 K. Example spectra simulated using this line list are shown and comparisons made to the existing data in the CDMS database. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases.

astro-ph.SR↗

arXiv2017

MARVEL analysis of the measured high-resolution rovibronic spectra of $^{48}$Ti$^{16}$O

Accurate, experimental rovibronic energy levels, with associated labels and uncertainties, are reported for 11 low-lying electronic states of the diatomic \TiO\ molecule, determined using the \Marvel\ (Measured Active Rotational-Vibrational Energy Levels) algorithm. All levels are based on lines corresponding to critically reviewed and validated high-resolution experimental spectra taken from 24 literature sources. The transition data are in the 2 $-$ 22,160 \cm{} region. Out of the 49,679 measured transitions, 43,885 are triplet-triplet, 5710 are singlet-singlet and 84 are triplet-singlet transitions. A careful analysis of the resulting experimental spectroscopic network (SN) allows 48,590 transitions to be validated. The transitions determine 93 vibrational band origins of \TiO\, including 71 triplet and 22 singlet ones. There are 276 (73) triplet-triplet (singlet-singlet) band-heads derived from \Marvel\ experimental energies, 123 (38) of which have never been assigned in low or high resolution experiments. The highest $J$ value, where $J$ stands for the total angular momentum, for which an energy level is validated is 163. The number of experimentally-derived triplet and singlet \TiO\ rovibrational energy levels is 8682 and 1882, respectively. The lists of validated lines and levels for \TiO\ are deposited in the Supporting Information to this paper.

astro-ph.SR↗

arXiv2016

ExoMol line lists XVIII. The high temperature spectrum of VO

An accurate line list, VOMYT, of spectroscopic transitions is presented for hot VO. The 13 lowest electronic states are considered. Curves and couplings are based on initial {\it ab initio} electronic structure calculations and then tuned using available experimental data. Dipole moment curves, used to obtain transition intensities, are computed using high levels of theory (e.g. MRCI/aug-cc-pVQZ using state-specific or minimal-state CAS for dipole moments). This line list contains over 277 million transitions between almost 640,000 energy levels. It covers the wavelengths longer than 0.29 $μ$m and includes all transitions from energy levels within the lowest nine electronic states which have energies less than 20,000 \cm{} to upper states within the lowest 13 electronic states which have energies below 50,000 \cm{}. The line lists give significantly increased absorption at infrared wavelengths compared to currently available VO line lists. The full line lists is made available in electronic form via the CDS database and at www.exomol.com.

astro-ph.SR↗

arXiv2016

Low-temperature chemistry using the R-matrix method

Techniques for producing cold and ultracold molecules are enabling the study of chemical reactions and scattering at the quantum scattering limit, with only a few partial waves contributing to the incident channel, leading to the observation and even full control of state-to-state collisions in this regime. A new R-matrix formalism is presented for tackling problems involving low- and ultra-low energy collisions. This general formalism is particularly appropriate for slow collisions occurring on potential energy surfaces with deep wells. The many resonance states make such systems hard to treat theoretically but offer the best prospects for novel physics: resonances are already being widely used to control diatomic systems and should provide the route to steering ultracold reactions. Our R-matrix-based formalism builds on the progress made in variational calculations of molecular spectra by using these methods to provide wavefunctions for the whole system at short internuclear distances, (a regime known as the inner region). These wavefunctions are used to construct collision energy-dependent R-matrices which can then be propagated to give cross sections at each collision energy. The method is formulated for ultracold collision systems with differing numbers of atoms.

physics.chem-ph↗

arXiv2016

Ab initio calculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

Accurate knowledge of the rovibronic near-infrared and visible spectra of vanadium monoxide (VO) is very important for studies of cool stellar and hot planetary atmospheres. Here, the required ab initio dipole moment and spin-orbit coupling curves for VO are produced. This data forms the basis of a new VO line list considering 13 different electronic states and containing over 277 million transitions. Open shell transition, metal diatomics are challenging species to model through ab initio quantum mechanics due to the large number of low-lying electronic states, significant spin-orbit coupling and strong static and dynamic electron correlation. Multi-reference configuration interaction methodologies using orbitals from a complete active space self-consistent-field (CASSCF) calculation are the standard technique for these systems. We use different state-specific or minimal-state CASSCF orbitals for each electronic state to maximise the calculation accuracy. The off-diagonal dipole moment controls the intensity of electronic transitions. We test finite-field off-diagonal dipole moments, but found that (1) the accuracy of the excitation energies were not sufficient to allow accurate dipole moments to be evaluated and (2) computer time requirements for perpendicular transitions were prohibitive. The best off-diagonal dipole moments are calculated using wavefunctions with different CASSCF orbitals.

physics.chem-ph↗

arXiv2016

The {\it ab initio} calculation of spectra of open shell diatomic molecules

The spectra (rotational, rotation-vibrational or electronic) of diatomic molecules due to transitions involving only closed-shell ($^1Σ$) electronic states follow very regular, simple patterns and their theoretical analysis is usually straightforward. On the other hand, open-shell electronic states lead to more complicated spectral patterns and, moreover, often appear as a manifold of closely lying electronic states, leading to perturbations with even larger complexity. This is especially true when at least one of the atoms is a transition metal. Traditionally these complex cases have been analysed using approaches based on perturbation theory, with semi-empirical parameters determined by fitting to spectral data. Recently the needs of two rather diverse scientific areas have driven the demand for improved theoretical models of open-shell diatomic systems based on an \emph{ab initio} approach, these areas are ultracold chemistry and the astrophysics of "cool" stars, brown dwarfs and most recently extrasolar planets. However, the complex electronic structure of these molecules combined with the accuracy requirements of high-resolution spectroscopy render such an approach particularly challenging. This review describes recent progress in developing methods for directly solving the effective Schrödinger equation for open-shell diatomic molecules, with a focus on molecules containing a transtion metal. It considers four aspects of the problem: 1. The electronic structure problem, 2. Non-perturbative treatments of the curve couplings, 3. The solution of the nuclear motion Schrödinger equation, 4. The generation of accurate electric dipole transition intensities. Examples of applications are used to illustrate these issues.

physics.chem-ph↗

arXiv2011

Quantum entanglement between electronic and vibrational degrees of freedom in molecules

We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with a tendency towards double welled potentials using model coupled harmonic diabatic potential-energy surfaces. The von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions in such a bipartite system. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local minima). However, in this region two distinct types of entanglement are found: (1) entanglement that arises purely from the degeneracy of energy levels in the two potential wells and which is destroyed by slight asymmetry, and (2) entanglement that involves strongly interacting states in each well that is relatively insensitive to asymmetry. These two distinct regions are termed fragile degeneracy-induced entanglement and persistent entanglement, respectively. Six classic molecular systems describable by two diabatic states are considered: ammonia, benzene, semibullvalene, pyridine excited triplet states, the Creutz-Taube ion, and the radical cation of the "special pair" of chlorophylls involved in photosynthesis. These chemically diverse systems are all treated using the same general formalism and the nature of the entanglement that they embody is elucidated.

quant-ph↗