Publications 20242025-04-28T11:10:50+02:00

Publications (2024)

Total peer-reviewed articles: 132

The role of intersystem crossing in the reactive collision of S+(4S) with H2

Authors: Zanchet, Alexandre; Roncero, Octavio; Karabulut, Ezman; Solem, Nicolas; Romanzin, Claire; Thissen, Roland; Alcaraz, Christian

Journal: JOURNAL OF CHEMICAL PHYSICS

Publication date: 2024/07/28

DOI: 10.1063/5.0214447

Abstract: We report a study on the reactive collision of S+(S-4) with H-2, HD, and D-2 combining guided ion beam experiments and quantum-mechanical calculations. It is found that the reactive cross sections reflect the existence of two different mechanisms, one being spin-forbidden. Using different models, we demonstrate that the spin-forbidden pathway follows a complex mechanism involving three electronic states instead of two as previously thought. The good agreement between theory and experiment validates the methodology employed and allows us to fully understand the reaction mechanism. This study also provides new fundamental insights into the intersystem crossing process. (c) 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution-NonCommercial 4.0International (CC BY-NC) license (https://creativecommons.org/licenses/by-nc/4.0/).

Low-lying Negative Ion States Probed in Potassium – Ethanol Collisions

Authors: Lozano, Ana Isabel; Kumar, Sarvesh; Pereira, Pedro J. S.; Kerkeni, Boutheina; Garcia, Gustavo; Limao-Vieira, Paulo

Journal: CHEMPHYSCHEM

Publication date: 2024/07/15

DOI: 10.1002/cphc.202400314

Abstract: Dissociative electron transfer in collisions between neutral potassium atoms and neutral ethanol molecules yields mainly OH-, followed by C2H5O-, O-, CH3- and CH2-. The dynamics of negative ions have been investigated by recording time-of-flight mass spectra in a wide range of collision energies from 17.5 to 350 eV in the lab frame, where the branching ratios show a relevant energy dependence for low/intermediate collision energies. The dominant fragmentation channel in the whole energy range investigated has been assigned to the hydroxyl anion in contrast to oxygen anion from dissociative electron attachment (DEA) experiments. This result shows the relevant role of the electron donor in the vicinity of the temporary negative ion formed allowing access to reactions which are not thermodynamically attained in DEA experiments. The electronic state spectroscopy of such negative ions, was obtained from potassium cation energy loss spectra in the forward scattering direction at 205 eV impact energy, showing a prevalent Feshbach resonance at 9.36 +/- 0.10 eV with sigma OH*/sigma CH* ${{sigma }_{OH}<^>{<^>{ast}}/{sigma }_{CH}<^>{<^>{ast}}}$ character, while a less pronounced sigma OH* ${{sigma }_{OH}<^>{<^>{ast}}}$ contribution assigned to a shape resonance has been obtained at 3.16 +/- 0.10 eV. Quantum chemical calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom have been performed to support the experimental findings. A joint experimental and theoretical investigation on ethanol negative ion formation by charge transfer is reported for the first time. The electronic state spectroscopy of the lowest-lying anionic states is comprehensively discussed rendering special relevance to the role of the different shape and core-excited Feshbach resonances, while the fragmentation pattern shows significant differences from dissociative electron attachment experiments. image

Cyano-Polycyclic Aromatic Hydrocarbon Interstellar Candidates: Laboratory Identification, Equilibrium Structure and Astronomical Search of Cyanobiphenylene

Authors: Cabezas, Carlos; Janeiro, Jesus; Perez, Dolores; Li, Wenqin; Agundez, Marcelino; Steber, Amanda L.; Guitian, Enrique; Demaison, Jean; Perez, Cristobal; Cernicharo, Jose; Lesarri, Alberto

Journal: JOURNAL OF PHYSICAL CHEMISTRY LETTERS

Publication date: 2024/07/12

DOI: 10.1021/acs.jpclett.4c01500

Abstract: The interplay between laboratory rotational spectroscopy and radio astronomical observations provides the most effective procedure for identifying molecules in the interstellar medium (ISM). Following the recent interstellar detections of several Polycyclic Aromatic Hydrocarbons (PAHs) and cyano derivatives in the dense molecular cloud TMC-1, it is reasonable to consider searching for other cyano-PAHs in this astronomical source. We present a rotational spectroscopy investigation of the two cyano derivatives of the PAH biphenylene, a plausible reaction product of interstellar benzyne. The rotational spectrum provided molecular parameters for the parent species and 14 monosubstituted isotopologues for each isomer. An accurate equilibrium structure was determined for both isomers using Watson’s mass-dependence method (r(m)((2))), offering information on its uncommon ring union. Astronomical searches for the cyanobiphenylene isomers have been undertaken in TMC-1, using the QUIJOTE line survey. No lines of any isomer were found in this astronomical source, but the experimental data will serve to enable future searches for these species in the ISM.

In-depth exploration of catalytic sites on amorphous solid water: I. The astrosynthesis of aminomethanol

Authors: Bovolenta, Giulia M.; Silva-Vera, Gabriela; Bovino, Stefano; Molpeceres, German; Kaestner, Johannes; Vogt-Geisse, Stefan

Journal: PHYSICAL CHEMISTRY CHEMICAL PHYSICS

Publication date: 2024/07/10

DOI: 10.1039/d4cp01865f

Abstract: Chemical processes taking place on ice-grain mantles are pivotal to the complex chemistry of interstellar environments. In this study, we conducted a comprehensive analysis of the catalytic effects of an amorphous solid water (ASW) surface on the reaction between ammonia (NH3) and formaldehyde (H2CO) to form aminomethanol (NH2CH2OH) using density functional theory. We identified potential catalytic sites based on the binding energy distribution of NH3 and H2CO reactants, on a set-of-clusters surface model composed of 22 water molecules and found a total of 14 reaction paths. Our results indicate that the catalytic sites can be categorized into four groups, depending on the interactions of the carbonyl oxygen and the amino group with the ice surface in the reactant complex. A detailed analysis of the reaction mechanism using Intrinsic Reaction Coordinate and reaction force analysis, revealed three distinct chemical events for this reaction: formation of the C-N bond, breaking of the N-H bond, and formation of the O-H hydroxyl bond. Depending on the type of catalytic site, these events can occur within a single, concerted, albeit asynchronous, step, or can be isolated in a step-wise mechanism, with the lowest overall transition state energy observed at 1.3 kcal mol-1. A key requirement for the low-energy mechanism is the presence of a pair of dangling OH bonds on the surface, found at 5% of the potential catalytic sites on an ASW porous surface. Unfurling the reaction mechanism of aminomethanol formation on interstellar ice-grain mantles.

Static and spherically symmetric vacuum spacetimes with non-expanding principal null directions in f(R) gravity

Authors: Guilabert, Alberto; Calzada, Pelayo V.; Bargueno, Pedro; Miret-Artes, Salvador

Journal: EUROPEAN PHYSICAL JOURNAL C

Publication date: 2024/07/09

DOI: 10.1140/epjc/s10052-024-13063-3

Abstract: In this work we characterize all the static and spherically symmetric vacuum solutions in f(R) gravity when the principal null directions of the Weyl tensor are non-expanding. In contrast to General Relativity, we show that the Nariai spacetime is not the only solution of this type when general f(R) theories are considered. In particular, we find four different solutions for the non-constant Ricci scalar case, all of them corresponding to the same theory, given by f (R)=r(0)(-1)|R-3/r(0)(2)|(1/2), where r0 is a non-null constant. Finally, we briefly present some geometric properties of these solutions.

Multiline study of the radial extent of SiO, CS, and SiS in asymptotic giant branch envelopes

Authors: Massalkhi, S.; Agundez, M.; Fonfria, J. P.; Pardo, J. R.; Velilla-Prieto, L.; Cernicharo, J.

Journal: ASTRONOMY & ASTROPHYSICS

Publication date: 2024/07/09

DOI: 10.1051/0004-6361/202450188

Abstract: Circumstellar envelopes around asymptotic giant branch (AGB) stars contain a rich diversity of molecules, whose spatial distribution is regulated by different chemical and physical processes. In the outer circumstellar layers, all molecules are efficiently destroyed due to interactions with interstellar ultraviolet photons. Here we aim to carry out a coherent and uniform characterization of the radial extent of three molecules (SiO, CS, and SiS) in envelopes around O- and C-rich AGB stars, and to study their dependence on mass-loss rate. To this end, we observed a reduced sample of seven M-type and seven C-type AGB envelopes in multiple lines of SiO, CS, and SiS with the Yebes 40 m and IRAM 30 m telescopes. The selected sources cover a wide range of mass-loss rates, from similar to 10(-7) M-circle dot yr(-1) to a few times 10(-5) M-circle dot yr(-1), and the observed lines cover a wide range of upper-level energies, from 2 K to 130 K. We carried out excitation and radiative transfer calculations over a wide parameter space in order to characterize the abundance and radial extent of each molecule. A chi(2) analysis indicates that the abundance is usually well constrained while the radial extent is in some cases more difficult to constrain. Our results indicate that the radial extent of the molecules considered here increases with increasing envelope density, in agreement with previous observational findings. At high envelope densities of (M) over dot/upsilon(infinity) > 10(-6) M-circle dot yr(-1) km(-1) s, SiO, CS, and SiS show a similar radial extent, while at low envelope densities of (M) over dot/upsilon(infinity) < 10(-7) M-circle dot yr(-1) km(-1) s, differences in radial extent appear among the three molecules, in agreement with theoretical expectations based on destruction due to photodissociation. At low envelope densities, we find a sequence of increasing radial extent, SiS -> CS -> SiO. We also find a tentative dependence of the radial extent on the chemical type (O- or C-rich) of the star for SiO and CS. Interferometric observations and further investigation of the photodissociation of SiO, CS, and SiS should provide clarification of the situation in regards to the relative photodissociation radii of SiO, CS, and SiS in AGB envelopes and their dependence on envelope density and C/O ratio.

Polycyclic aromatic hydrocarbon emission in galaxies as seen with JWST

Authors: Rigopoulou, D.; Donnan, F. R.; Garcia-Bernete, I; Pereira-Santaella, M.; Alonso-Herrero, A.; Davies, R.; Hunt, L. K.; Roche, P. F.; Shimizu, T.

Journal: MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY

Publication date: 2024/07/09

DOI: 10.1093/mnras/stae1535

Abstract: We present a systematic study of mid-infrared spectra of galaxies including star-forming galaxies and active galactic nuclei observed with JWST MIRI-MRS and NIRSpec-IFU. We focus on the relative variations of the 3.3, 6.2, 7.7, 11.3, 12.7, and 17 $mu$m polycyclic aromatic hydrocarbon (PAH) features within spatially resolved regions of galaxies including NGC 3256, NGC 7469, VV 114, II Zw96, and NGC 5728. Using theoretical PAH models and extending our earlier work, we introduce a new PAH diagnostic involving the 17 $mu$m PAH feature. To determine the drivers of PAH band variations in galaxies, we compare observed PAH spectral bands to predictions from theoretical PAH models. We consider extinction, dehydrogenation, and PAH size and charge as possible drivers of PAH band variations. We find a surprising uniformity in PAH size distribution among the spatially resolved regions of the galaxies studied here, with no evidence for preferential destruction of the smallest grains, contrary to earlier findings. Neither extinction nor dehydrogenation play a crucial role in setting the observed PAH bands. Instead, we find that PAH charge plays a significant role in PAH inter-band variations. We find a tight relation between PAH charge and the intensity of the radiation field as traced by the [Ne iii]$/$[Ne ii] maps. In agreement with recent JWST results, we find a predominance of neutral PAH molecules in the nuclei of active galaxies and their outflows. Ionized PAHs are the dominant population in star-forming galaxies. We discuss the implications of our findings for the use of PAHs as ISM tracers in high redshift galaxies.

Emergence of high-mass stars in complex fiber networks (EMERGE) I. Early ALMA Survey: Observations and massive data reduction

Authors: Hacar, A.; Socci, A.; Bonanomi, F.; Petry, D.; Tafalla, M.; Harsono, D.; Forbrich, J.; Alves, J.; Grossschedl, J.; Goicoechea, J. R.; Pety, J.; Burkert, A.; Li, G. X.

Journal: ASTRONOMY & ASTROPHYSICS

Publication date: 2024/07/05

DOI: 10.1051/0004-6361/202348565

Abstract: Context. Recent molecular surveys have revealed the rich gas organization of sonic-like filaments at small scales (so-called fibers) in all types of environments prior to the formation of low- and high-mass stars. These fibers form at the end of the turbulent cascade and are identified as the fine substructure within the hierarchical nature of the gas in the interstellar medium (ISM). Aims. Isolated fibers provide the subsonic conditions for the formation of low-mass stars. This paper introduces the Emergence of high-mass stars in complex fiber networks (EMERGE) project, which investigates whether complex fiber arrangements (networks) can also explain the origin of high-mass stars and clusters. Methods. We analyzed the EMERGE Early ALMA Survey including seven star-forming regions in Orion (OMC-1,2,3, and 4 South, LDN 1641N, NGC 2023, and the Flame Nebula) that were homogeneously surveyed in three molecular lines (N2H+ J = 1-0, HNC J = 1-0, and HC3N J = 10-9) and in the 3mm continuum using a combination of interferometric ALMA mosaics and IRAM-30m single-dish (SD) maps, together with a series of Herschel, Spitzer, and WISE archival data. We also developed a systematic data reduction framework allowing the massive data processing of ALMA observations. Results. We obtained independent continuum maps and spectral cubes for all our targets and molecular lines at different (SD and interferometric) resolutions, and we explored multiple data combination techniques. Based on our low-resolution (SD) observations (30 ” or similar to 12 000 au), we describe the global properties of our sample, which covers a wide range of physical conditions, including low- (OMC-4 South and NGC 2023), intermediate (OMC-2, OMC-3, and LDN 1641N), and high-mass (OMC-1 and Flame Nebula) star-forming regions in different evolutionary stages. The comparison between our single-dish maps and ancillary YSO catalogs denotes N2H+ (1-0) as the best proxy for the dense, star-forming gas in our targets, which show a constant star formation efficiency and a fast time evolution of less than or similar to 1 Myr. While apparently clumpy and filamentary in our SD data, all targets show a much more complex fibrous substructure at the enhanced resolution of our combined ALMA+IRAM-30m maps (4.” 5 or similar to 2000 au). A large number of filamentary features at subparsec scales are clearly recognized in the high-density gas (greater than or similar to 10(5) cm(-3)) that is traced by N2H+ (1-0) directly connected to the formation of individual protostars. Surprisingly, this complex gas organization appears to extend farther into the more diffuse gas (similar to 10(3)-10(4) cm(-3)) traced by HNC (1-0). Conclusions. This paper presents the EMERGE Early ALMA Survey, which includes a first data release of continuum maps and spectral products for this project that are to be analysed in future papers of this series. A first look at these results illustrates the need of advanced data combination techniques between high-resolution interferometric (ALMA) and high-sensitivity, low-resolution single-dish (IRAM-30 m) datasets to investigate the intrinsic multiscale, gas structure of the ISM.

Rate coefficients for the O + H2 and O + D2 reactions: how well ring polymer molecular dynamics accounts for tunelling

Authors: Menendez, Marta; Veselinova, Anzhela; Zanchet, Alexandre; Jambrina, Pablo G.; Aoiz, F. Javier

Journal: PHYSICAL CHEMISTRY CHEMICAL PHYSICS

Publication date: 2024/07/05

DOI: 10.1039/d4cp01711k

Abstract: We present here extensive calculations of the O(P-3) + H-2 and O(P-3) + D-2 reaction dynamics spanning the temperature range from 200 K to 2500 K. The calculations have been carried out using fully converged time-independent quantum mechanics (TI QM), quasiclassical trajectories (QCT) and ring polymer molecular dynamics (RPMD) on the two lowest lying adiabatic potential energy surfaces (PESs), 1(3)A ‘ and 1(3)A ”, calculated by Zanchet et al. [J. Chem. Phys., 2019, 151, 094307]. TI QM rate coefficients were determined using the cumulative reaction probability formalism on each PES including all of the total angular momenta and the Coriolis coupling and can be considered to be essentially exact within the Born-Oppenheimer approximation. The agreement between the rate coefficients calculated by using QM and RPMD is excellent for the reaction with D-2 in almost the whole temperature range. For the reaction with H-2, although the agreement is very good above 500 K, the deviations are significant at lower temperatures. In contrast, the QCT calculations largely underestimate the rate coefficients for the two isotopic variants due to their inability to account for tunelling. The differences found in the disagreements between RPMD and QM rate coefficients for the reactions for both the isotopologues are indicative of the ability of the RPMD method to accurately describe systems where tunelling plays a relevant role. Considering that both reactions are dominated by tunelling below 500 K, the present results show that RPMD is a very powerful tool for determining rate coefficients. The present QM rate coefficients calculated on adiabatic PESs slightly underestimate the best global fits of the experimental measurements, which we attribute to the intersystem crossing with the singlet 1(1)A ‘ PES.

Temporal entropy and the complexity of computing the expectation value of local operators after a quench

Authors: Carignano, Stefano; Marimon, Carlos Ramos; Tagliacozzo, Luca

Journal: PHYSICAL REVIEW RESEARCH

Publication date: 2024/07/03

DOI: 10.1103/PhysRevResearch.6.033021

Abstract: We study the computational complexity of simulating the time-dependent expectation value of a local operator in a one-dimensional quantum system by using temporal matrix product states(MPSs) and argue that it is intimately related to that of encoding temporal transition matrices and their partial traces. We show that we can upper-bound the rank of these reduced transition matrices by one of the Heisenberg evolution of local operators, thus making aconnection between two apparently different quantities, the temporal entanglement and the local operator entanglement(OE). As a result, whenever the local OE grows slower than linearly in time, we show that computing time-dependent expectation values of local operators using temporal MPSs is likely advantageous with respect to computing the same quantities using standard MPS techniques.

Computational Modeling: Up-to-Date Approaches and Cutting-Edge Applications from Clusters, Nanostructures to Bulk Systems

Authors: Prosmiti, Rita; Gonzalez-Lezana, Tomas

Journal: CHEMPHYSCHEM

Publication date: 2024/07/02

DOI: 10.1002/cphc.202400207

Abstract: The contributions in this special theme collection, in honor to Prof. P. Villarreal, cover a broad variety of computational methodologies and experimental techniques, containing studies on gas phase, clusters and condensed phase systems. image

PDRs4All VIII. Mid-infrared emission line inventory of the Orion Bar

Authors: Van De Putte, Dries; Meshaka, Raphael; Trahin, Boris; Habart, Emilie; Peeters, Els; Berne, Olivier; Alarcon, Felipe; Canin, Amelie; Chown, Ryan; Schroetter, Ilane; Sidhu, Ameek; Boersma, Christiaan; Bron, Emeric; Dartois, Emmanuel; Goicoechea, Javier R.; Gordon, Karl D.; Onaka, Takashi; Tielens, Alexander G. G. M.; Verstraete, Laurent; Wolfire, Mark G.; Abergel, Alain; Bergin, Edwin A.; Bernard-Salas, Jeronimo; Cami, Jan; Cuadrado, Sara; Dicken, Daniel; Elyajouri, Meriem; Fuente, Asuncion; Joblin, Christine; Khan, Baria; Lacinbala, Ozan; Languignon, David; Le Gal, Romane; Maragkoudakis, Alexandros; Okada, Yoko; Pasquini, Sofia; Pound, Marc W.; Robberto, Massimo; Rollig, Markus; Schefter, Bethany; Schirmer, Thiebaut; Tabone, Benoit; Vicente, Silvia; Zannese, Marion; Colgan, Sean W. J.; He, Jinhua; Rouille, Gael; Togi, Aditya; Aleman, Isabel; Auchettl, Rebecca; Baratta, Giuseppe Antonio; Bejaoui, Salma; Bera, Partha P.; Black, John H.; Boulanger, Francois; Bouwman, Jordy; Brandl, Bernhard; Brechignac, Philippe; Brunken, Sandra; Buragohain, Mridusmita; Burkhardt, Andrew; Candian, Alessandra; Cazaux, Stephanie; Cernicharo, Jose; Chabot, Marin; Chakraborty, Shubhadip; Champion, Jason; Cooke, Ilsa R.; Coutens, Audrey; Cox, Nick L. J.; Demyk, Karine; Meyer, Jennifer Donovan; Foschino, Sacha; Garcia-Lario, Pedro; Gerin, Maryvonne; Gottlieb, Carl A.; Guillard, Pierre; Gusdorf, Antoine; Hartigan, Patrick; Herbst, Eric; Hornekaer, Liv; Issa, Lina; Jager, Cornelia; Janot-Pacheco, Eduardo; Kannavou, Olga; Kaufman, Michael; Kemper, Francisca; Kendrew, Sarah; Kirsanova, Maria S.; Klaassen, Pamela; Kwok, Sun; Labiano, Alvaro; Lai, Thomas S. -Y.; Le Floch, Bertrand; Le Petit, Franck; Li, Aigen; Linz, Hendrik; Mackie, Cameron J.; Madden, Suzanne C.; Mascetti, Joelle; McGuire, Brett A.; Merino, Pablo; Micelotta, Elisabetta R.; Morse, Jon A.; Mulas, Giacomo; Neelamkodan, Naslim; Ohsawa, Ryou; Omont, Alain; Paladini, Roberta; Palumbo, Maria Elisabetta; Pathak, Amit; Pendleton, Yvonne J.; Petrignani, Annemieke; Pino, Thomas; Puga, Elena; Rangwala, Naseem; Rapacioli, Mathias; Rho, Jeonghee; Ricca, Alessandra; Roman-Duval, Julia; Roser, Joseph; Roueff, Evelyne; Salama, Farid; Sales, Dinalva A.; Sandstrom, Karin; Sarre, Peter; Sciamma-O’Brien, Ella; Sellgren, Kris; Shenoy, Sachindev S.; Teyssier, David; Thomas, Richard D.; Witt, Adolf N.; Wootten, Alwyn; Ysard, Nathalie; Zettergren, Henning; Zhang, Yong; Zhang, Ziwei E.; Zhen, Junfeng

Journal: ASTRONOMY & ASTROPHYSICS

Publication date: 2024/07/02

DOI: 10.1051/0004-6361/202449295

Abstract: Context. Mid-infrared emission features are important probes of the properties of ionized gas and hot or warm molecular gas, which are difficult to probe at other wavelengths. The Orion Bar photodissociation region (PDR) is a bright, nearby, and frequently studied target containing large amounts of gas under these conditions. Under the PDRs4All Early Release Science Program for JWST, a part of the Orion Bar was observed with MIRI integral field unit (IFU) spectroscopy, and these high-sensitivity IR spectroscopic images of very high angular resolution (0.2 ”) provide a rich observational inventory of the mid-infrared (MIR) emission lines, while resolving the H II region, the ionization front, and multiple dissociation fronts. Aims. We list, identify, and measure the most prominent gas emission lines in the Orion Bar using the new MIRI IFU data. An initial analysis summarizes the physical conditions of the gas and demonstrates the potential of these new data and future IFU observations with JWST. Methods. The MIRI IFU mosaic spatially resolves the substructure of the PDR, its footprint cutting perpendicularly across the ionization front and three dissociation fronts. We performed an up-to-date data reduction, and extracted five spectra that represent the ionized, atomic, and molecular gas layers. We identified the observed lines through a comparison with theoretical line lists derived from atomic data and simulated PDR models. The identified species and transitions are summarized in the main table of this work, with measurements of the line intensities and central wavelengths. Results. We identified around 100 lines and report an additional 18 lines that remain unidentified. The majority consists of H I recombination lines arising from the ionized gas layer bordering the PDR. The H I line ratios are well matched by emissivity coefficients from H recombination theory, but deviate by up to 10% because of contamination by He I lines. We report the observed emission lines of various ionization stages of Ne, P, S, Cl, Ar, Fe, and Ni. We show how the Ne III/Ne II, S IV/S III, and Ar III/Ar II ratios trace the conditions in the ionized layer bordering the PDR, while Fe III/Fe II and Ni III/Ni II exhibit a different behavior, as there are significant contributions to Fe II and Ni II from the neutral PDR gas. We observe the pure-rotational H-2 lines in the vibrational ground state from 0-0 S (1) to 0-0 S (8), and in the first vibrationally excited state from 1-1 S (5) to 1-1 S (9). We derive H-2 excitation diagrams, and for the three observed dissociation fronts, the rotational excitation can be approximated with one thermal (similar to 700 K) component representative of an average gas temperature, and one nonthermal component (similar to 2700 K) probing the effect of UV pumping. We compare these results to an existing model of the Orion Bar PDR, and find that the predicted excitation matches the data qualitatively, while adjustments to the parameters of the PDR model are required to reproduce the intensity of the 0-0 S (6) to S (8) lines.

PDRs4All IX. Sulfur elemental abundance in the Orion Bar

Authors: Fuente, Asuncion; Roueff, Evelyne; Le Petit, Franck; Le Bourlot, Jacques; Bron, Emeric; Wolfire, Mark G.; Babb, James F.; Yan, Pei-Gen; Onaka, Takashi; Black, John H.; Schroetter, Ilane; Van De Putte, Dries; Sidhu, Ameek; Canin, Amelie; Trahin, Boris; Alarcon, Felipe; Chown, Ryan; Kannavou, Olga; Berne, Olivier; Habart, Emilie; Peeters, Els; Goicoechea, Javier R.; Zannese, Marion; Meshaka, Raphael; Okada, Yoko; Roellig, Markus; Le Gal, Romane; Sales, Dinalva A.; Palumbo, Maria Elisabetta; Baratta, Giuseppe Antonio; Madden, Suzanne C.; Neelamkodan, Naslim; Zhang, Ziwei E.; Stancil, P. C.

Journal: ASTRONOMY & ASTROPHYSICS

Publication date: 2024/07/02

DOI: 10.1051/0004-6361/202449229

Abstract: Context. One of the main problems in astrochemistry is determining the amount of sulfur in volatiles and refractories in the interstellar medium. The detection of the main sulfur reservoirs (icy H2S and atomic gas) has been challenging, and estimates are based on the reliability of models to account for the abundances of species containing less than 1% of the total sulfur. The high sensitivity of the James Webb Space Telescope provides an unprecedented opportunity to estimate the sulfur abundance through the observation of the [S I] 25.249 mu m line. Aims. Our aim is to determine the amount of sulfur in the ionized and warm molecular phases toward the Orion Bar as a template to investigate sulfur depletion in the transition between the ionized gas and the molecular cloud in HII regions. Methods. We used the [S III] 18.7 mu m, [S IV] 10.5 mu m, and [S 1] 25.249 mu m lines to estimate the amount of sulfur in the ionized and molecular gas along the Orion Bar. For the theoretical part, we used an upgraded version of the Meudon photodissociation region (PDR) code to model the observations. New inelastic collision rates of neutral atomic sulfur with ortho-and para- molecular hydrogen were calculated to predict the line intensities. Results. The [S III] 18.7 mu m and [S IV] 10.5 mu m lines are detected over the imaged region with a shallow increase (by a factor of 4) toward the HII region. This suggests that their emissions are partially coming from the Orion Veil. We estimate a moderate sulfur depletion, by a factor of similar to 2, in the ionized gas. The corrugated interface between the molecular and atomic phases gives rise to several edge-on dissociation fronts we refer to as DF1, DF2, and DF3. The [S 1] 25.249 mu m line is only detected toward DF2 and DF3, the dissociation fronts located farthest from the HII region. This is the first ever detection of the [S 1] 25.249 mu m line in a PDR. The detailed modeling of DF3 using the Meudon PDR code shows that the emission of the [S 1] 25.249 mu m line is coming from warm (>40 K) molecular gas located at A(V) similar to 1-5 mag from the ionization front. Moreover, the intensity of the [S 1] 25.249 mu m line is only accounted for if we assume the presence of undepleted sulfur. Conclusions. Our data show that sulfur remains undepleted along the ionic, atomic, and molecular gas in the Orion Bar. This is consistent with recent findings that suggest that sulfur depletion is low in massive star-forming regions because of the interaction of the UV photons coming from the newly formed stars with the interstellar matter.

Parameter estimation from quantum-jump data using neural networks

Authors: Rinaldi, Enrico; Lastre, Manuel Gonzalez; Herreros, Sergio Garcia; Ahmed, Shahnawaz; Khanahmadi, Maryam; Nori, Franco; Munoz, Carlos Sanchez

Journal: QUANTUM SCIENCE AND TECHNOLOGY

Publication date: 2024/07/01

DOI: 10.1088/2058-9565/ad3c68

Abstract: We present an inference method utilizing artificial neural networks for parameter estimation of a quantum probe monitored through a single continuous measurement. Unlike existing approaches focusing on the diffusive signals generated by continuous weak measurements, our method harnesses quantum correlations in discrete photon-counting data characterized by quantum jumps. We benchmark the precision of this method against Bayesian inference, which is optimal in the sense of information retrieval. By using numerical experiments on a two-level quantum system, we demonstrate that our approach can achieve a similar optimal performance as Bayesian inference, while drastically reducing computational costs. Additionally, the method exhibits robustness against the presence of imperfections in both measurement and training data. This approach offers a promising and computationally efficient tool for quantum parameter estimation with photon-counting data, relevant for applications such as quantum sensing or quantum imaging, as well as robust calibration tasks in laboratory-based settings.

An Ab Initio Journey toward the Molecular-Level Understanding and Predictability of Subnanometric Metal Clusters

Authors: de Lara-Castells, Maria Pilar

Journal: SMALL STRUCTURES

Publication date: 2024/06/30

DOI: 10.1002/sstr.202400147

Abstract: Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied molecule-like electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom-scale modeling using either density functional theory (DFT) or methods at a high level of ab initio theory, even addressing nonadiabatic (e.g., Jahn-Teller) effects. Surface-supported AMCs can be routinely modeled using DFT, enabling long real-time molecular dynamics simulations. Their optical properties can also be addressed using time-dependent DFT or reduced density matrix (RDM) theory. These theoretical-computational efforts aim to achieve predictability and molecular-level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of ab initio and DFT-based modeling is illustrated through recent studies of unsupported and surface-supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state-of-the-art. This perspective presents a vision of subnanometric metal clusters from first-principles. It includes fundamental concepts aimed to understand their unique fluxional behavior, the unexpected reversible oxidation of the smallest copper clusters, the enhancement of the optical and photocatalytic properties of titanium dioxide surfaces acting as their supports, and discussing future challenges in their ab initio modelling beyond the state-of-the-art.image (c) 2024 WILEY-VCH GmbH

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