arXiv subjects

P. B. Rimmer

Publications and source records attributed to P. B. Rimmer.

16 recordsLinked to original sources

arXiv2026

A Comprehensive Sulfur Chemistry Network Including Excited S(1D) and SO(1Δ) for the XODIAC Photochemical Model: Accounting for Missing Sulfur Processes in Venus and Exo-Venus Analogs

Sulfur chemistry plays a central role in controlling the atmospheric structure, cloud formation, and composition of Venus and Venus-like exoplanets. However, key reactions involving ground- and excited-state sulfur species remain poorly constrained, and existing photochemical models often rely on incomplete or uncertain kinetic data under high-temperature, CO2-rich conditions. In this work, we compute kinetic parameters for reactions of ground-state S(3P) and excited-state S(1D) with CO2 under Venus-like conditions, forming SO(3Sigma), SO(1Delta), and CO. We characterize the underlying potential energy surfaces, identify intermediate complexes, and derive temperature-dependent rate coefficients using a master-equation framework based on the chemically significant eigenvalue method. We also provide NASA 7-term polynomial coefficients for S and SO in both ground and excited states to enable consistent incorporation into photochemical models. Incorporating these reactions into the one-dimensional photochemical model XODIAC for Venus produces only minor effects above 60 km due to competing pathways. While the model reproduces most observed sulfur species, discrepancies remain for S3 and S4. Introducing a 1 ppm near-surface atomic sulfur source, representing unresolved deep-atmosphere or surface processes, enhances S3 and S4 abundances by 1-2 orders of magnitude and improves agreement with observations. For exo-Venus analogs, the updated chemistry produces modest changes under isothermal conditions. In contrast, in strongly irradiated atmospheres with a high-altitude isotherm and a near-surface sulfur source, it leads to pronounced changes in most sulfur-bearing species, along with significant enhancements in S(1D) and SO(1Delta). These results highlight missing sulfur pathways, including excited states and deep sources, and potential implications for shaping Venus and exo-Venus atmospheres.

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arXiv2025

Cosmic ray ionisation of a post-impact early Earth atmosphere: Solar cosmic ray ionisation must be considered in origin-of-life scenarios

Cosmic rays (CR), both solar and Galactic, have an ionising effect on the Earth's atmosphere and are thought to be important for prebiotic molecule production. In particular, the $\rm{H_2}$-dominated atmosphere following an ocean-vaporising impact is considered favourable to prebiotic molecule formation. We model solar and Galactic CR transport through a post-impact early Earth atmosphere at 200Myr. We aim to identify the differences in the resulting ionisation rates, $ζ$, particularly at the Earth's surface during a period when the Sun was very active. We use a Monte Carlo model to describe CR transport through the early Earth atmosphere, giving the CR spectra as a function of altitude. We calculate $ζ$ and the ion-pair production rate, $Q$, as a function of altitude due to Galactic and solar CR. The Galactic and solar CR spectra are both affected by the Sun's rotation rate, $Ω$, because the solar wind velocity and magnetic field strength both depend on $Ω$ and influence CR transport. We consider a range of input spectra resulting from the range of possible $Ω$, from $3.5-15\, Ω_{\rm{\odot}}$. To account for the possibility that the Galactic CR spectrum outside the Solar System varies over Gyr timescales, we compare top-of-atmosphere $ζ$ resulting from two different scenarios. We also consider the suppression of the CR spectra by a planetary magnetic field. We find that $ζ$ and $Q$ due to CR are dominated by solar CR in the early Earth atmosphere for most cases. The corresponding $ζ$ at the early Earth's surface ranges from $5 \times 10^{-21}\rm{s^{-1}}$ for $Ω= 3.5\,Ω_{\rm{\odot}}$ to $1 \times 10^{-16}\rm{s^{-1}}$ for $Ω= 15\,Ω_{\rm{\odot}}$. Thus if the young Sun was a fast rotator, it is likely that solar CR had a significant effect on the chemistry at the Earth's surface at the time when life is likely to have formed.

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arXiv2025

Exploring the atmosphere of GJ 1132 b with CRIRES+

With a mass, radius, and mean density similar to Earth's, the rocky planet GJ 1132 b is the first truly small planet for which an atmosphere detection was proposed. If confirmed, ultra-reduced magma outgassing is the only mechanism capable of producing HCN and H$_2$O in large enough quantities to match the HST observations. The proposed atmosphere detection, however was challenged by reanalysis of the same HST data by different teams. Recent JWST observations returned ambiguous results due to the unaccounted for variability seen between two different visits. Here we report the analysis of three CRIRES+ transit observations of GJ 1132 b in order to determine the presence or absence of He I, HCN, CH$_4$, and H$_2$O in its atmosphere. We are unable to detect the presence of any of these species in the atmosphere of GJ 1132 b assuming a clear, H$_2$-dominated atmosphere, although we can place upper limits for the volume mixing ratios of CH$_4$, HCN, and H$_2$O using injections tests and atmospheric retrievals. These retrieved upper limits show the capability of CRIRES+ to detecting chemical species in rocky exoplanets, if the atmosphere is H$_2$ dominated. The detection of the atmospheres of small planets with high mean molecular weight, and the capability to distinguish between the variability introduced by stellar activity and/or the planetary atmosphere will require high-resolution spectrographs in the upcoming extremely large telescopes.

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arXiv2024

Shedding a Light on the Kinetics of the Carboxysulfitic Scenario

One way in which we can attempt to relate chemical pathways to geochemical environments is by studying the kinetics of a given sequence of reactions and identifying the conditions under which this chemistry is the most productive. Many prebiotic reactions rely on a source of fixed carbon, therefore chemical pathways that suggest prebiotically plausible ways of fixing carbon are of significant interest. One such pathway is the carboxysulfitic reaction network which uses solvated electrons, produced as a result of electron photodetachment from sulfite, to reduce carbon. In this work we explore carboxysulfitic chemistry at three different pH values: 6, 9, and 12. We utilise a new light source, that matches the broadband spectral shape of the young Sun, to irradiate a mixture of bicarbonate and sulfite. We determine the rate equation for the production of formate from these compounds and find the order to be 0.71 $\pm$ 0.12 with respect to bicarbonate and -0.60 $\pm$ 0.10 with respect to sulfite. Following this, we determine rate constants for the production of formate considering two different mechanisms. We find this chemistry to be feasible at all three of the pH values tested, with the magnitude of the rate constants being highly dependent on the assumed mechanism. We suggest that these results may have implications for Mars Sample Return owing to Jezero Crater having had lakes similar to those in which we propose carboxysulfitic chemistry to have been the most productive. Due to Mars' relatively unaltered surface, we propose that Mars Sample Return missions could look for preserved tracers of this chemistry, shedding light on Mars' past conditions and its potential for having hosted life.

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arXiv2023

The energetic particle environment of a GJ 436 b-like planet

A key first step to constrain the impact of energetic particles in exoplanet atmospheres is to detect the chemical signature of ionisation due to stellar energetic particles and Galactic cosmic rays. We focus on GJ$\,$436, a well-studied M dwarf with a warm Neptune-like exoplanet. We demonstrate how the maximum stellar energetic particle momentum can be estimated from the stellar X-ray luminosity. We model energetic particle transport through the atmosphere of a hypothetical exoplanet at orbital distances between $a=0.01-0.2\,$au from GJ$\,$436, including GJ$\,$436$\,$b's orbital distance (0.028$\,$au). For these distances we find that, at top-of-atmosphere, stellar energetic particles ionise molecular hydrogen at a rate of $ζ_{\rm StEP,H_2} \sim 4\times10^{-10}-2\times10^{-13}\,\mathrm{s^{-1}}$. In comparison, Galactic cosmic rays alone lead to $ζ_{\rm GCR, H_2}\sim2\times 10^{-20}-10^{-18} \,\mathrm{s^{-1}}$. At 10au we find that ionisation due to Galactic cosmic rays equals that of stellar energetic particles: $ζ_{\rm GCR,H_2} = ζ_{\rm StEP,H_2} \sim 7\times10^{-18}\,\rm{s^{-1}}$ for the top-of-atmosphere ionisation rate. At GJ$\,$436$\,$b's orbital distance, the maximum ion-pair production rate due to stellar energetic particles occurs at pressure $P\sim 10^{-3}\,$bar while Galactic cosmic rays dominate for $P>10^2\,$bar. These high pressures are similar to what is expected for a post-impact early Earth atmosphere. The results presented here will be used to quantify the chemical signatures of energetic particles in warm Neptune-like atmospheres.

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arXiv2022

Linking atmospheric chemistry of the hot Jupiter HD 209458b to its formation location through infrared transmission and emission spectra

The elemental ratios of carbon, nitrogen, and oxygen in the atmospheres of hot Jupiters may hold clues to their formation locations in the protostellar disc. In this work, we adopt gas phase chemical abundances of C, N and O from several locations in a disc chemical kinetics model as sources for the envelope of the hot Jupiter HD 209458b and evolve the planet's atmospheric composition using a 1D chemical kinetics model, treating both vertical mixing and photochemistry. We consider two atmospheric pressure-temperature profiles, one with and one without a thermal inversion. From each of the resulting 32 atmospheric composition profiles, we find that the molecules CH4, NH3, HCN, and C2H2 are more prominent in the atmospheres computed using a realistic non-inverted P-T profile in comparison to a prior equilibrium chemistry based work which used an analytical P-T profile. We also compute the synthetic transmission and emission spectra for these atmospheres and find that many spectral features vary with the location in the disc where the planet's envelope was accreted. By comparing with the species detected using the latest high-resolution ground-based observations, our model suggests HD 209458b could have accreted most of its gas between the CO2 and CH4 icelines with a super solar C/O ratio from its protostellar disc, which in turn directly inherited its chemical abundances from the protostellar cloud. Finally, we simulate observing the planet with the James Webb Space Telescope (JWST) and show that differences in spectral signatures of key species can be recognized. Our study demonstrates the enormous importance of JWST in providing new insights into hot Jupiter's formation environments.

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arXiv2022

Reduced atmospheres of post-impact worlds: The early Earth

Impacts may have had a significant effect on the atmospheric chemistry of the early Earth. Reduced phases in the impactor (e.g., metallic iron) can reduce the planet's H$_2$O inventory to produce massive atmospheres rich in H$_2$. Whilst previous studies have focused on the interactions between the impactor and atmosphere in such scenarios, we investigate two further effects, 1) the distribution of the impactor's iron inventory during impact between the target interior, target atmosphere, and escaping the target, and 2) interactions between the post-impact atmosphere and the impact-generated melt phase. We find that these two effects can potentially counterbalance each other, with the melt-atmosphere interactions acting to restore reducing power to the atmosphere that was initially accreted by the melt phase. For a $\sim10^{22}\,\mathrm{kg}$ impactor, when the iron accreted by the melt phase is fully available to reduce this melt, we find an equilibrium atmosphere with H$_2$ column density $\sim10^4\,\mathrm{moles\,cm^{-2}}$ ($p\mathrm{H2}\sim120\,\mathrm{bars}\mathrm{,}~X_\mathrm{H2}\sim0.77$), consistent with previous estimates. However, when the iron is not available to reduce the melt (e.g., sinking out in large diameter blobs), we find significantly less H$_2$ ($7\times10^2-5\times10^3\,\mathrm{moles\,cm^{-2}}$, $p\mathrm{H2}\lesssim60\,\mathrm{bars}\mathrm{,}~X_\mathrm{H2}\lesssim0.41$). These lower H$_2$ abundances are sufficiently high that species important to prebiotic chemistry can form (e.g., NH3, HCN), but sufficiently low that the greenhouse heating effects associated with highly reducing atmospheres, which are problematic to such chemistry, are suppressed. The manner in which iron is accreted by the impact-generated melt phase is critical in determining the reducing power of the atmosphere and re-solidified melt pool in the aftermath of impact.

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arXiv2021

Stellar versus Galactic: The intensity of energetic particles at the evolving Earth and young exoplanets

Energetic particles may have been important for the origin of life on Earth by driving the formation of prebiotic molecules. We calculate the intensity of energetic particles, in the form of stellar and Galactic cosmic rays, that reach Earth at the time when life is thought to have begun ($\sim$3.8Gyr ago), using a combined 1.5D stellar wind model and 1D cosmic ray model. We formulate the evolution of a stellar cosmic ray spectrum with stellar age, based on the Hillas criterion. We find that stellar cosmic ray fluxes are larger than Galactic cosmic ray fluxes up to $\sim$4 GeV cosmic ray energies $\sim$3.8Gyr ago. However, the effect of stellar cosmic rays may not be continuous. We apply our model to HR 2562b, a young warm Jupiter-like planet orbiting at 20au from its host star where the effect of Galactic cosmic rays may be observable in its atmosphere. Even at 20au, stellar cosmic rays dominate over Galactic cosmic rays.

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arXiv2020

The Galactic cosmic ray intensity at the evolving Earth and young exoplanets

Cosmic rays may have contributed to the start of life on Earth. Here, we investigate the evolution of the Galactic cosmic ray spectrum at Earth from ages $t = 0.6-6.0\,$Gyr. We use a 1D cosmic ray transport model and a 1.5D stellar wind model to derive the evolving wind properties of a solar-type star. At $t=1\,$Gyr, approximately when life is thought to have begun on Earth, we find that the intensity of $\sim$GeV Galactic cosmic rays would have been $\sim10$ times smaller than the present-day value. At lower kinetic energies, Galactic cosmic ray modulation would have been even more severe. More generally, we find that the differential intensity of low energy Galactic cosmic rays decreases at younger ages and is well described by a broken power-law in solar rotation rate. We provide an analytic formula of our Galactic cosmic ray spectra at Earth's orbit for different ages. Our model is also applicable to other solar-type stars with exoplanets orbiting at different radii. Specifically, we use our Galactic cosmic ray spectrum at 20$\,$au for $t=600\,$Myr to estimate the penetration of cosmic rays in the atmosphere of HR$\,$2562b, a directly imaged exoplanet orbiting a young solar-type star. We find that the majority of particles $<0.1$GeV are attenuated at pressures $\gtrsim10^{-5}\,$bar and thus do not reach altitudes below $\sim100\,$km. Observationally constraining the Galactic cosmic ray spectrum in the atmosphere of a warm Jupiter would in turn help constrain the flux of cosmic rays reaching young Earth-like exoplanets.

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arXiv2019

Identifiable Acetylene Features Predicted for Young Earth-like Exoplanets with Reducing Atmospheres undergoing Heavy Bombardment

The chemical environments of young planets are assumed to be largely influenced by impacts of bodies lingering on unstable trajectories after the dissolution of the protoplanetary disk. We explore the chemical consequences of impacts within the context of reducing planetary atmospheres dominated by carbon monoxide, methane and molecular nitrogen. A terawatt high-power laser was selected in order to simulate the airglow plasma and blast wave surrounding the impactor. The chemical results of these experiments are then applied to a theoretical atmospheric model. The impact simulation results in substantial volume mixing ratios within the reactor of 5% hydrogen cyanide (HCN), 8% acetylene (C$_2$H$_2$), 5% cyanoacetylene (HC$_3$N) and 1% ammonia (NH$_3$). These yields are combined with estimated impact rates for the Early Earth to predict surface boundary conditions for an atmospheric model. We show that impacts might have served as sources of energy that would have led to steady-state surface quantities of 0.4% C$_2$H$_2$, 400 ppm HCN and 40 ppm NH$_3$. We provide simulated transit spectra for an Earth-like exoplanet with this reducing atmosphere during and shortly after eras of intense impacts. We predict that acetylene is as observable as other molecular features on exoplanets with reducing atmospheres that have recently gone through their own `Heavy Bombardments', with prominent features at 3.05 $μ$m and 10.5 $μ$m.

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arXiv2019

A spectral survey of an ultra-hot Jupiter: Detection of metals in the transmission spectrum of KELT-9 b

Context: KELT-9 b exemplifies a newly emerging class of short-period gaseous exoplanets that tend to orbit hot, early type stars - termed ultra-hot Jupiters. The severe stellar irradiation heats their atmospheres to temperatures of $\sim 4,000$ K, similar to the photospheres of dwarf stars. Due to the absence of aerosols and complex molecular chemistry at such temperatures, these planets offer the potential of detailed chemical characterisation through transit and day-side spectroscopy. Studies of their chemical inventories may provide crucial constraints on their formation process and evolution history. Aims: To search the optical transmission spectrum of KELT-9 b for absorption lines by metals using the cross-correlation technique. Methods: We analyse 2 transits observed with the HARPS-N spectrograph. We use an isothermal equilibrium chemistry model to predict the transmission spectrum for each of the neutral and singly-ionized atoms with atomic numbers between 3 and 78. Of these, we identify the elements that are expected to have spectral lines in the visible wavelength range and use those as cross-correlation templates. Results: We detect absorption of Na I, Cr II, Sc II and Y II, and confirm previous detections of Mg I, Fe I, Fe II and Ti II. In addition, we find evidence of Ca I, Cr I, Co I, and Sr II that will require further observations to verify. The detected absorption lines are significantly deeper than model predictions, suggesting that material is transported to higher altitudes where the density is enhanced compared to a hydrostatic profile. There appears to be no significant blue-shift of the absorption spectrum due to a net day-to-night side wind. In particular, the strong Fe II feature is shifted by $0.18 \pm 0.27$ km~s$^{-1}$, consistent with zero. Using the orbital velocity of the planet we revise the steller and planetary masses and radii.

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arXiv2016

Ionisation and discharge in cloud-forming atmospheres of brown dwarfs and extrasolar planets

Brown dwarfs and giant gas extrasolar planets have cold atmospheres with a rich chemical compositions from which mineral cloud particles form. Their properties, like particle sizes and material composition, vary with height, and the mineral cloud particles are charged due to triboelectric processes in such dynamic atmospheres. The dynamics of the atmospheric gas is driven by the irradiating host star and/or by the rotation of the objects that changes during its lifetime. Thermal gas ionisation in these ultra-cool but dense atmospheres allows electrostatic interactions and magnetic coupling of a substantial atmosphere volume. Combined with a strong magnetic field $\gg B_{\rm Earth}$, a chromosphere and aurorae might form as suggested by radio and X-ray observations of brown dwarfs. Non-equilibrium processes like cosmic ray ionisation and discharge processes in clouds will increase the local pool of free electrons in the gas. Cosmic rays and lighting discharges also alter the composition of the local atmospheric gas such that tracer molecules might be identified. Cosmic rays affect the atmosphere through air showers which was modelled with a 3D Monte Carlo radiative transfer code to be able to visualise their spacial extent. Given a certain degree of thermal ionisation of the atmospheric gas, we suggest that electron attachment to charge mineral cloud particles is too inefficient to cause an electrostatic disruption of the cloud particles. Cloud particles will therefore not be destroyed by Coulomb explosion for the local temperature in the collisional dominated brown dwarf and giant gas planet atmospheres. However, the cloud particles are destroyed electrostatically in regions with strong gas ionisation. The potential size of such cloud holes would, however, be too small and might occur too far inside the cloud to mimic the effect of, e.g., magnetic field induced star spots.

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arXiv2014

Multiwaveband photometry of the irradiated brown dwarf WD0137-349B

WD0137-349 is a white dwarf-brown dwarf binary system in a 116 minute orbit. We present radial velocity observations and multiwaveband photometry from V, R and I in the optical, to J, H and Ks in the near-IR and [3.6], [4.5], [5.8] and [8.0] microns in the mid-IR. The photometry and lightcurves show variability in all wavebands, with the amplitude peaking at [4.5] microns, where the system is also brightest. Fluxes and brightness temperatures were computed for the heated and unheated atmosphere of the brown dwarf (WD0137-349B) using synthetic spectra of the white dwarf using model atmosphere simulations. We show that the flux from the brown dwarf dayside is brighter than expected in the Ks and [4.5] micron bands when compared to models of irradiated brown dwarfs with full energy circulation and suggest this over-luminosity may be attributed to H2 fluorescence or H3+ being generated in the atmosphere by the UV irradiation.

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arXiv2014

Disk evolution, element abundances and cloud properties of young gas giant planets

We discuss the chemical pre-conditions for planet formation, in terms of gas and ice abundances in a protoplanetary disk, as function of time and position, and the resulting chemical composition and cloud properties in the atmosphere when young gas giant planets form. Large deviations between the abundances of the host star and its gas giants seem likely to occur if the planet formation follows the core-accretion scenario. These deviations stem from the separate evolution of gas and dust in the disk, where the dust forms the planet cores, followed by the final run-away accretion of the left-over gas. ProDiMo protoplanetary disk models are used to predict the chemical evolution of gas and ice in the midplane. We find that cosmic rays play a crucial role in slowly un-blocking the CO, where the liberated oxygen forms water, which then freezes out quickly. Therefore, the C/O ratio in the gas phase is found to gradually increase with time, in a region bracketed by the water and CO ice-lines. In this regions, C/O is found to approach unity after about 5 Myrs, scaling with the cosmic ray ionisation rate. We then explore how the atmospheric chemistry and cloud properties in young gas giants are affected when the non-solar C/O ratios predicted by the disk models are assumed. The DRIFT cloud formation model is applied to study the formation of atmospheric clouds under the influence of varying primordial element abundances and its feedback onto the local gas. We demonstrate that element depletion by cloud formation plays a crucial role in converting an oxygen-rich atmosphere gas into carbon-rich gas when non-solar, primordial element abundances are considered as suggested by disk model.

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arXiv2013

The Influence of Galactic Cosmic Rays on Ion-Neutral Hydrocarbon Chemistry in the Upper Atmospheres of Free-Floating Exoplanets

Cosmic rays may be linked to the formation of volatiles necessary for prebiotic chemistry. We explore the effect of cosmic rays in a hydrogen-dominated atmosphere, as a proof-of-concept that ion-neutral chemistry may be important for modelling hydrogen-dominated atmospheres. In order to accomplish this, we utilize Monte Carlo cosmic ray transport models with particle energies of $10^6$ eV $< E < 10^{12}$ eV in order to investigate the cosmic ray enhancement of free electrons in substellar atmospheres. Ion-neutral chemistry is then applied to a Drift-Phoenix model of a free-floating giant gas planet. Our results suggest that the activation of ion-neutral chemistry in the upper atmosphere significantly enhances formation rates for various species, and we find that C$_2$H$_2$, C$_2$H$_4$, NH$_3$, C$_6$H$_6$ and possibly C$_{10}$H are enhanced in the upper atmospheres because of cosmic rays. Our results suggest a potential connection between cosmic ray chemistry and the hazes observed in the upper atmospheres of various extrasolar planets. Chemi-ionization reactions are briefly discussed, as they may enhance the degree of ionization in the cloud layer.

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arXiv2011

Observing a column-dependent zeta in dense interstellar sources: the case of the Horsehead Nebula

Context: Observations of small carbon-bearing molecules such as CCH, C4H, c-C3H2, and HCO in the Horsehead Nebula have shown these species to have higher abundances towards the edge of the source than towards the center. Aims: Given the determination of a wide range of values for zeta (s-1), the total ionization rate of hydrogen atoms, and the proposal of a column-dependent zeta(N_H), where N_H is the total column of hydrogen nuclei, we desire to determine if the effects of zeta(N_H) in a single object with spatial variation can be observable. We chose the Horsehead Nebula because of its geometry and high density. Method: We model the Horsehead Nebula as a near edge-on photon dominated region (PDR), using several choices for zeta, both constant and as a function of column. The column-dependent zeta functions are determined by a Monte Carlo model of cosmic ray penetration, using a steep power-law spectrum and accounting for ionization and magnetic field effects. We consider a case with low-metal elemental abundances as well as a sulfur-rich case. Results: We show that use of a column-dependent zeta(N_H) of 5(-15) s-1 at the surface and 7.5(-16) s-1 at Av = 10 on balance improves agreement between measured and theoretical molecular abundances, compared with constant values of zeta.

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