Photodissociation Rates Research Articles

Ru-terpyridine complexes containing clotrimazole as potent photoactivatable selective antifungal agents

The overuse of antimicrobial agents in medical and veterinary applications has led to the development of antimicrobial resistance in some microorganisms and this is now one of the major concerns in modern society. In this context, the use of transition metal complexes with photoactivatable properties, which can act as drug delivery systems triggered by light, could become a potent strategy to overcome the problem of resistance. In this work several Ru complexes with terpyridine ligands and the clotrimazole fragment, which is a potent antimycotic drug, were synthesized. The main goal was to explore the potential photoactivated activity of the complexes as antifungal agents and evaluate the effect of introducing different substituents on the terpyridine ligand. The complexes were capable of delivering the clotrimazole unit upon irradiation with visible light in a short period of time. The influence of the substituents on the photodissociation rate was explained by means of TD-DFT calculations. The complexes were tested against three different yeasts, which were selected based on their prevalence in fungal infections. The complex in which a carboxybenzene unit was attached to the terpyridine ligand showed the best activity against the three species under light, with minimal inhibitory concentration values of 0.88 μM and a phototoxicity index of 50 achieved. The activity of this complex was markedly higher than that of free clotrimazole, especially upon irradiation with visible light (141 times higher). The complexes were more active on yeast species than on cancer cell lines.

High Accuracy Photodissociation Rates in VULCAN with MCRT

Photochemical processing is a key influence on the chemical compositions of exoplanet atmospheres. We develop a 1D plane-parallel Monte Carlo radiative-transfer (MCRT) path length method to calculate actinic fluxes for photochemical modeling, which we couple to the VULCAN photochemical model. Due to the flexible nature of MCRT methods, this enables accurate calculation of photodissociation rates for complex multiple scattering scenarios encountered in exoplanet atmospheres such as high altitude haze layers.

Ultraviolet H2luminescence in molecular clouds induced by cosmic rays

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions.Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux.Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H2by electron impact, and of photodissociation and photoionisation cross sections.Results. We calculated the H2level population of each rovibrational level of theX, B, C, B′,D, B″,D′, andastates. We then computed the UV photon spectrum of H2in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H2column density, the isomeric H2composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C2H2, C2H3, C3H3, LiH, N2, NaCl, NaH, O2+, S2, SiH, l-C4, and l-C5H. A special focus is given to the photoionisation rates of H2, HF, and N2, as well as to the photodissociation of H2, which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H2column density, as well as the dust properties.

H i in Molecular Clouds: Irradiation by FUV Plus Cosmic Rays

We extend the analytic theory presented by Sternberg et al. and Bialy & Sternberg for the production of atomic hydrogen (H i) via far-ultraviolet (FUV) photodissociation at the boundaries of dense interstellar molecular (H2) clouds to also include the effects of penetrating (low-energy) cosmic rays (CRs) for the growth of the total H i column densities. We compute the steady-state abundances of the H i and H2 in one-dimensional gas slabs in which the FUV photodissociation rates are reduced by depth-dependent H2 self-shielding and dust absorption and the CR ionization rates are either constant or reduced by transport effects. The solutions for the H i and H2 density profiles and the integrated H i columns depend primarily on the ratios I UV/Rn and ζ/Rn, where I UV is the intensity of the photodissociating FUV field, ζ is the H2 CR ionization rate, n is the hydrogen gas density, and R is the dust surface H2 formation rate coefficient. We present computations for a wide range of FUV field strengths, CR ionization rates, and dust-to-gas ratios. We develop analytic expressions for the growth of the H i column densities. For Galactic giant molecular clouds (GMCs) with multiphased (warm/cold) H i envelopes, the interior CR zones will dominate the production of the H i only if s−1, where M GMC is the GMC mass, and including attenuation of the CR fluxes. For most Galactic GMCs and conditions, FUV photodissociation dominates over CR ionization for the production of the H i column densities. Furthermore, the CRs do not affect the H i-to-H2 transition points.

A Theoretical Study of Temperature-dependent Photodissociation Cross Sections and Rates for O2

The photodissociation of O2 is thought to play a vital role in blocking UV radiation in the Earth’s atmosphere and likely has great importance in characterizing exoplanetary atmospheres. This work considers four photodissociation processes of O2 associated with its four electronic states, whose potential energy curves and transition dipole moments are calculated at the icMRCI+Q/aug-cc-pwCV5Z-DK level of theory. The quantum-mechanical approach is used to compute the state-resolved cross sections for two triplet transitions from the ground X state to the excited B and E states, and for two singlet transitions from the a 1Δg and b states to the 1 1Πu state, with a consideration of photon wavelengths from 500 Å to the relevant threshold. Assuming the populations of the initial states satisfy a Boltzmann distribution, the temperature-dependent photodissociation cross sections are estimated at gas dynamic temperatures of 0–10,000 K, in which the discrete progressions of the B and E transitions are also considered. The photodissociation rates of O2 in the interstellar, solar, and blackbody radiation fields are also calculated using the temperature-dependent cross sections. The resulting photodissociation cross sections and rates are important for the atmospheric chemistry of Earth and may be also useful for the atmospheric exploration of exoplanets.

Simulation-guided engineering of split GFPs with efficient β-strand photodissociation

Green fluorescent proteins (GFPs) are ubiquitous for protein tagging and live-cell imaging. Split-GFPs are widely used to study protein-protein interactions by fusing proteins of interest to split GFP fragments that create a fluorophore upon typically irreversible complementation. Thus, controlled dissociation of the fragments is desirable. Although we have found that split strands can be photodissociated, the quantum efficiency of light-induced photodissociation of split GFPs is low. Traditional protein engineering approaches to increase efficiency, including extensive mutagenesis and screening, have proved difficult to implement. To reduce the search space, key states in the dissociation process are modeled by combining classical and enhanced sampling molecular dynamics with QM/MM calculations, enabling the rational design and engineering of split GFPs with up to 20-fold faster photodissociation rates using non-intuitive amino acid changes. This demonstrates the feasibility of modeling complex molecular processes using state-of-the-art computational methods, and the potential of integrating computational methods to increase the success rate in protein engineering projects.

The atmospheric oxidizing capacity in China – Part 1: Roles of different photochemical processes

Abstract. Atmospheric oxidation capacity (AOC) characterizes the ability of the atmosphere to scavenge air pollutants. However, the processes involved in China, where anthropogenic emissions have changed dramatically in the past decade, are not fully understood. A detailed analysis of different parameters that determine the AOC in China is presented on the basis of numerical simulations performed with the regional chemical–meteorological Weather Research and Forecasting model with Chemistry (WRF-Chem). The model shows that the aerosol effects related to extinction and heterogeneous processes produce a decrease in surface ozone of approximately 8–10 ppbv in NOx-limited rural areas and an increase of 5–10 ppbv in VOC-limited urban areas. In this latter case, the ozone increase is noticeable for aerosol concentrations ranging from 20 to 45 µg m−3 in July 2018. The ozone reduction in NOx-sensitive regions is due to the combined effect of nitrogen dioxide and peroxy radical uptake on particles and of the light extinction by aerosols, which affects the photodissociation rates. The ozone increase in VOC-sensitive areas is attributed to the uptake of NO2 by aerosols, which is offset by the reduced ozone formation associated with HO2 uptake and with aerosol extinction. Our study concludes that more than 90 % of the daytime AOC is due to the reaction of the hydroxyl radical with VOCs and carbon monoxide. In urban areas, during summertime, the main contributions to daytime AOC are the reactions of OH with alkene (30 %–50 %), oxidized volatile organic compounds (OVOCs) (33 %–45 %), and carbon monoxide (20 %–45 %). In rural areas, the largest contribution results from the reaction of OH with alkenes (60 %). Nocturnal AOC is dominantly attributed to the reactions with the nitrate radical (50 %–70 %). Our results shed light on the contribution of aerosol-related NOx loss and the high reactivity of alkenes for photochemical pollution. With the reduction in aerosols and anthropogenic ozone precursors, the chemistry of nitrogen and temperature-sensitive VOCs will become increasingly important. More attention needs to be paid to the role of photodegradable OVOCs and nocturnal oxidants in the formation of secondary pollutants.

Photodissociation cross sections and rates of NaO

ABSTRACT Photodissociation of NaO may be important for the sodium chemistry in various astrophysical regions. This work produces the photodissociation cross sections and rates of NaO over the temperature range from 0 to 15 000 K. First, the state-resolved cross sections for transitions from the ground and first excited states of NaO are investigated using ab initio potential energy curves and transition dipole moments. The temperature-dependent cross sections were then obtained by assuming a Boltzmann distribution to describe the population of the initial state. Detailed comparisons with experimental cross sections at 200 and 300 K reveal that the X 2Π → 1 2∆ and X 2Π → 2 2Σ− transitions may be the main photodissociation pathways for NaO in the wavelengths of about 2400–2580 Å, while the X 2Π → B 2Σ− transition may play a dominant role in the wavelengths of about 3534–4230 Å. Finally, photodissociation rates in the interstellar, solar, and blackbody radiation fields were determined. In the interstellar and solar radiation fields, the X 2Π → B 2Σ− transition dominates at low temperatures and the A 2Σ+ → 2 2Σ+ transition dominates at high temperatures. The total photodissociation rates in ultraviolet-rich and visible-rich radiation fields are almost insensitive to the temperature. The photodissociation cross sections and rates of NaO should be useful for investigating the chemical evolution of the sodium element in planetary exospheres, atmospheres of cool stars, and envelopes of evolved stars.

Air Temperature Intermittency and Photofragment Excitation

Four observational results: the intermittency of air temperature; its correlation with ozone photodissociation rate; the diurnal variation of ozone in the upper stratosphere; and the cold bias of meteorological analyses compared to observations, are reviewed. The excitation of photofragments and their persistence of velocity after collision is appealed to as a possible explanation. Consequences are discussed, including the interpretation of the Langevin equation and fluctuation–dissipation in the atmosphere, the role of scale invariance and statistical multifractality, and what the results might mean for the distribution of isotopes among atmospheric molecules. An adjunct of the analysis is an exponent characterizing jet streams. Observational tests are suggested.

Photodissociation and photoionization of molecules of astronomical interest

Context. Vacuum-ultraviolet (VUV) photons are important drivers of chemical processes in space. Thus, it is important to accurately characterize and constrain photorates in different radiation fields, via the photodissociation and photoionization cross sections of individual atoms and molecules. These have been available in the Leiden VUV photodissocation and photoionization cross section database. Aims. Experimental and theoretical advances in the past decade or so have allowed multiple new cross sections to be obtained, particularly photoionization cross sections of radicals. The database is hereby updated by including these more recent cross sections and is also expanded with several astronomically relevant species. Methods. The cross sections have been used to calculate photodissociation and photoionization rates in several different radiation fields as well as from cosmic-ray-induced VUV fluxes. The reduction of rates in shielded regions was calculated as a function of dust, molecular and atomic hydrogen, atomic carbon, and self-shielding column densities. The relative importance of these shielding types is molecule and atom dependent, as well as the assumed dust absorbance. All the data are publicly available from the Leiden VUV cross section database. Results. The Leiden VUV cross section database has been updated with 14 new astrophysically relevant molecular species and 16 updates to previous entries. The database update is accompanied by a brief review of the basic physical processes, particularly photoionization processes which have not been reviewed in the context of previous database updates.

Conformational-Dependent Photodissociation of Glycolic Acid in an Argon Matrix

Ultraviolet-induced photodissociation and photo-isomerization of the three most stable conformers (SSC, GAC, and AAT) of glycolic acid are investigated in a low-temperature solid argon matrix using FTIR spectroscopy and employing laser radiation with wavelengths of 212 nm, 226 nm, and 230 nm. The present work broadens the wavelength range of photochemical studies of glycolic acid, thus extending the understanding of the overall photochemistry of the compound. The proposed kinetic model for the photodissociation of glycolic acid proceeds from the lowest energy conformer (SSC). The model suggests that ultraviolet light induces isomerization only between the SSC and GAC conformers and between the SSC and AAT conformers. The relative reaction rate coefficients are reported for all proposed reactions. These results suggest that the direct photodissociation of GAC and AAT conformer does not occur in an argon matrix. The main photodissociation channel via the SSC conformer produces formaldehyde–water complexes. The proposed photodissociation mechanism emphasizes that the conformers’ relative abundancies can significantly affect the photodissociation rate of the molecule. For example, in the case of high relative GAC and AAT concentrations, the ultraviolet photodissociation of glycolic acid requires the proceeding photo-isomerization of GAC and AAT to SSC.

Flat-optics hybrid MoS2/polymer films for photochemical conversion.

Novel light harvesting platforms and strategies are crucial to develop renewable photon to energy conversion technologies that overcome the current global energy and environmental challenges. Two-dimensional (2D) transition metal dichalcogenide (TMD) semiconductor layers are particularly attractive for photoconversion applications but new ultra-compact photon harvesting schemes are urgently required to mitigate their poor photon absorption properties. Here, we propose a flat-optics scheme based on nanogrooved ultra-thin MoS2 layers conformally grown onto large area (cm2 scale) nanopatterned templates. The subwavelength re-shaping of the 2D-TMD layers promotes the excitation of photonic Rayleigh anomaly (RA) modes, uniquely boosting a strong in-plane electromagnetic confinement. By tailoring the illumination conditions, we demonstrate effective tuning of the photonic anomalies over a broadband visible spectrum across the absorption band of relevant polluting dye molecules. Thanks to the strong photonic in-plane confinement, we achieve a resonant enhancement of the photodissociation rate of methylene blue (MB) molecules, well above a factor of 2. These results highlight the potential of flat-optics photon harvesting schemes for boosting photoconversion efficiency in large-scale hybrid 2D-TMD/polymer layers, with a strong impact in various applications ranging from new-generation photonics to waste water remediation and renewable energy storage.

Molecular-excited-state calculations with the qubit-excitation-based adaptive variational quantum eigensolver protocol

Calculations of molecular spectral properties, like photodissociation rates and absorption bands, rely on knowledge of the excited state energies of the molecule of interest. Protocols based on the variational quantum eigensolver (VQE) are promising candidates to calculate such energies on emerging noisy intermediate-scale quantum (NISQ) computers. The successful implementation of these protocols on NISQ computers, relies on ans\"atze that can accurately approximate the molecular states and that can be implemented by shallow quantum circuits. We introduce the excited qubit-excitation-based adaptive (e-QEB-ADAPT)-VQE protocol to calculate molecular-excited-state energies. The e-QEB-ADAPT-VQE constructs efficient problem-tailored ans\"atze by iteratively appending evolutions of qubit excitation operators. The e-QEB-ADAPT-VQE also improves on previous ADAPT-VQE protocol in that it is designed to be independent on the choice of initial reference state. We perform classical numerical simulations for LiH and ${\mathrm{BeH}}_{2}$ to benchmark the performance of the e-QEB-ADAPT-VQE. We demonstrate that the e-QEB-ADAPT-VQE can construct highly accurate ans\"atze that require at least an order of magnitude fewer cnot gates than standard fixed unitary coupled-cluster ans\"atze, such as the UCCSD and the GUCCSD. We also show that the e-QEB-ADAPT-VQE is more successful in constructing ans\"atze for excited molecular states than other ADAPT-VQE protocols.

An ab initio study for the photodissociation of HCl and HF

ABSTRACT Detailed studies of HCl and HF photodissociation are required for an in-depth understanding the chlorine and fluorine chemistry in Venus and exoplanets. Here, we present an ab initio study of photodissociation of HCl and HF. Except for the widely studied A 1Π←X 1Σ+ photodissociation process, the ground-state photodissociation processes for HCl and HF via higher excited states are considered. State-resolved cross-sections are computed for nine photodissociation processes of HCl from a total of 871 ground rovibrational levels. For HF, seven photodissociation processes are considered for the computation of state-resolved cross-sections from all the rovibrational levels in the ground state. Subsequently, temperature-dependent cross-sections for the considered transition processes of HCl and HF are estimated from 0 to 10 000 K with a grid of 34 temperatures. Careful comparisons with the recent ExoMol study and the Leiden Observatory database are made. The photodissociation rates in the interstellar and blackbody radiation fields are also discussed.

Multireference configuration interaction study of the predissociation of C2 via its F1Πu state.

Photodissociation is one of the main destruction pathways for dicarbon (C2) in astronomical environments, such as diffuse interstellar clouds, yet the accuracy of modern astrochemical models is limited by a lack of accurate photodissociation cross sections in the vacuum ultraviolet range. C2 features a strong predissociative F1Πu-X1Σg + electronic transition near 130nm originally measured in 1969; however, no experimental studies of this transition have been carried out since, and theoretical studies of the F1Πu state are limited. In this work, potential energy curves of excited electronic states of C2 are calculated with the aim of describing the predissociative nature of the F1Πu state and providing new ab initio photodissociation cross sections for astrochemical applications. Accurate electronic calculations of 56 singlet, triplet, and quintet states are carried out at the DW-SA-CASSCF/MRCI+Q level of theory with a CAS(8,12) active space and the aug-cc-pV5Z basis set augmented with additional diffuse functions. Photodissociation cross sections arising from the vibronic ground state to the F1Πu state are calculated by a coupled-channel model. The total integrated cross section through the F1Πu v = 0 and v = 1 bands is 1.198 × 10-13 cm2 cm-1, giving rise to a photodissociation rate of 5.02 × 10-10 s-1 under the standard interstellar radiation field, much larger than the rate in the Leiden photodissociation database. In addition, we report a new 21Σu + state that should be detectable via a strong 21Σu +-X1Σg + band around 116nm.

ExoMol photodissociation cross-sections – I. HCl and HF

ABSTRACT Photon initiated chemistry, 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 data base of cross-sections is discussed.

Photodissociation Rate, Excess Energy, and Kinetic Total Energy Release for the Photolysis of H2O Producing O(1S) by Solar UV Radiation Field

Forbidden atomic oxygen lines in emission are ubiquitous for cometary spectra in the visible region, and the oxygen atoms in metastable states causing the forbidden emission lines are considered as a proxy of H2O in coma. However, the photodissociation rate and related quantities for the dissociation reaction producing O(1S) from H2O have never been estimated based on experimental studies. Based on the recent laboratory study of the photodissociation reaction of H2O producing O(1S) by Chang et al., we derived the photodissociation rates of the reactions for both the O(1S) and O(1D) channels, consistent with the green-to-red line ratios observed in comets so far. Furthermore, the total kinetic energies released for the photodissociation products are also consistent with the intrinsic line widths of forbidden atomic oxygen emission lines observed in comets. The photodissociation rates of H2O leading to O(1S) and O(1D) calculated here do not significantly change the previous estimates of CO2/H2O in comets based on the green-to-red line ratios of the comets if we use the photodissociation rates of CO2 (calculated elsewhere) with a correction for the difference of solar UV spectra used for calculating photodissociation rates of H2O and CO2.

Destruction of AlF: a quantum study of its ground-state photodissociation

ABSTRACTPhotodissociation by ultraviolet photons is the key destruction pathway for aluminium monofluoride (AlF) in the envelope of the carbon star IRC +10216 from the stellar photosphere up to the outer layers. However, there is no available photodissociation data for AlF, which hampers the prediction of the abundances of Al-bearing molecules in astrochemical models. Here, we present an ab initio study of AlF photodissociation. Potential energy curves of seven singlet states for AlF were computed by the internally contracted multireference single and double configuration-interaction method and aug-cc-pCV5Z-DK basis set, along with the transition dipole moments from excited singlet states to the ground state. State-resolved cross sections for the direct photodissociation from 36 349 ground rovibrational levels ( υ″≤120, J″≤360) to six singlet excited states were calculated by the quantum mechanical method. We found that the 21Π←X 1Σ+, 31Π←X 1Σ+, and 41Π←X 1Σ+ transitions have extremely strong absorption for lower wavelengths, especially between the Lyman and Lyman α ones. Photodissociation cross sections in local thermal equilibrium were estimated for gas temperatures from 500 to 20 000 K. Finally, the cross sections were utilized to calculate the photodissociation rates in the interstellar and blackbody radiation fields. The obtained photodissociation cross sections and rates can be used to determine the abundance of AlF in astrochemical models.

Energy deposition in Saturn’s equatorial upper atmosphere

We construct Saturn equatorial neutral temperature and density profiles of H, H2, He, and CH4, between 10−12 and 1 bar using measurements from Cassini’s Ion Neutral Mass Spectrometer (INMS) taken during the spacecraft’s final plunge into Saturn’s atmosphere on 15 September 2017, combined with previous deeper atmospheric measurements from the Cassini Composite InfraRed Spectrometer (CIRS) and from the UltraViolet Imaging Spectrograph (UVIS). These neutral profiles are fed into an energy deposition model employing soft X-ray and Extreme UltraViolet (EUV) solar fluxes at a range of spectral resolutions (Δλ=4×10−3nm to 1 nm) assembled from TIMED/SEE, from SOHO/SUMER, and from the Whole Heliosphere Interval (WHI) quiet Sun campaign. Our energy deposition model calculates ion production rate profiles through photo-ionisation and electron-impact ionisation processes, as well as rates of photo-dissociation of CH4. The ion reaction rate profiles we determine are important to obtain accurate ion density profiles, meanwhile methane photo-dissociation is key to initiate complex organic chemical processes. We assess the importance of spectral resolution in the energy deposition model by using a high-resolution H2 photo-absorption cross section, which has the effect of producing additional ionisation peaks near 800 km altitude. We find that these peaks are still formed when using low-resolution (Δλ=1nm) or mid-resolution (Δλ=0.1nm) solar spectra, as long as high-resolution cross sections are included in the model.

Temperature-dependent direct photodissociation cross sections and rates of AlCl

ABSTRACT The photodissociation process of aluminium monochloride (AlCl) plays an important role in modelling the chemistry of the circumstellar envelope. In this work, direct photodissociation cross sections of AlCl have been computed for transitions from the ground X1Σ+ state to six low-lying excited electronic states by using ab initio potential energy curves and transition dipole moments, which are obtained by the internally contracted multireference configuration-interaction method with Davidson correction and the aug-cc-pV6Z basis set. State-resolved cross sections for transitions from 38 958 rovibrational levels (υ″ ≤ 100, J″ ≤ 400) of the ground X1Σ+ state have been obtained for photon wavelengths from 500 Å to the dissociation threshold. Photodissociation cross sections in local thermal equilibrium are evaluated for gas temperatures from 500 to 10 000 K. Using the computed cross sections, temperature-dependent photodissociation rates of AlCl in the interstellar and blackbody radiation fields are determined. The results can be applied to the investigation of the chemical evolution of Al in the envelope of carbon-rich and oxygen-rich stars.