arXiv subjects

Masashi Tsuge

Publications and source records attributed to Masashi Tsuge.

14 recordsLinked to original sources

arXiv2026

H$_2$ Ortho-Para Spin Conversion on Inhomogeneous Grain Surfaces. II. impact of the rotational energy difference between adsorbed ortho-H$_2$ and para-H$_2$ and implication to deuterium fractionation chemistry

We investigate how the H$_2$ ortho-to-para ratio (OPR) and dueterium fractionation in star-forming regions are affected by nuclear spin conversion (NSC) on dust grains. Particular focus is placed on the rotational energy difference between ortho-H$_2$ (o-H$_2$) and para-H$_2$ (p-H$_2$) on grain surfaces. While the ground state of o-H$_2$ has a higher rotational energy than that of p-H$_2$ by 170.5 K in the gas phase, this energy difference is expected to become smaller on solid surfaces, where interactions between the surface and adsorbed H$_2$ molecules affect their rotational motion. A previous study by Furuya et al. (2019) developed a rigorous formulation of the rate for the temporal variation of the H$_2$ OPR via the NSC on grains, assuming that adsorbed o-H$_2$ has higher rotational energy than adsorbed p-H$_2$ by 170.5 K, as in the gas phase. In this work, we relax the assumption and re-evaluate the rate, varying the rotational energy difference between their ground states. The re-evaluated rate is incorporated into a gas-ice astrochemical model to study the evolution of the H$_2$ OPR and the deuterium fractionation in prestellar cores and the outer, cold regions of protostellar envelopes. The inclusion of the NSC on grains reduces the timescale of the H2 OPR evolution and thus the deuterium fractionation, at densities of >10$^4$ cm$^{-3}$ and temperatures of <14-16 K (depending on the rotational energy difference), when the ionization rate of H$_2$ is 10$^{-17}$ s$^{-1}$.

astro-ph.GA↗

arXiv2026

Methanol Formation via the Radical-radical Reaction of OH and CH3 Radicals Undergoing Transient Diffusion on Ice at 10 to 60 K

Methanol (CH3OH) is thought to form on interstellar ice dust via successive hydrogenation reactions. The reaction between CH3 and OH radicals could also conceivably generate methanol at temperatures above approximately 20 K, at which temperature hydrogen atoms will not adhere to the ice surface. However, this process has not been verified by well-controlled experiments. Using a newly-developed Cs+ ion pickup technique, the authors investigated the reaction between CH3 and OH radicals on the surface of amorphous solid water, an ice dust analogue, at temperatures from 10 to 60 K. In the present experiments, OH radicals were generated by UV photolysis of water molecules, following which methane (CH4) gas was deposited on the ice substrate. The results show that CH3OH was formed on the ice surface through the sequential reactions CH4 + OH -> CH3 + H2O and CH3 + OH -> CH3OH even at 10 K. Considering the very low surface coverage of reactants in the experimental condition, the second reaction was found to occur as a result of transient diffusion of CH3 due to the heat of the first reaction.

astro-ph.GA↗

arXiv2025

Formation of unsaturated carbon chains through carbon chemisorption on solid CO

The interaction of carbon atoms with solid carbon monoxide (CO) is a fundamental process in astrochemistry, influencing the formation of complex organic molecules in interstellar environments. This study investigates the adsorption and reaction mechanisms of carbon atoms on solid CO under cryogenic conditions, employing a combination of experimental techniques, including photostimulated desorption and resonance-enhanced multiphoton ionization (PSD-REMPI) and infrared spectroscopy, alongside quantum chemical calculations. The results reveal the formation of oxygenated carbon chains, such as CCO, C$_3$O$_2$, and C$_5$O$_2$, as well as CO$_2$. The findings highlight the role of chemisorption and subsequent reactions in driving molecular complexity on solid CO, with implications for the chemical evolution of interstellar ices and the potential formation of prebiotic molecules.

astro-ph.GA↗

arXiv2024

Methane Formation Efficiency on Icy Grains: Role of Adsorption States

Methane (CH4) is one of the major components of the icy mantle of cosmic dust prevalent in cold, dense regions of interstellar media, playing an important role in the synthesis of complex organic molecules and prebiotic molecules. Solid CH4 is considered to be formed via the successive hydrogenation of C atoms accreting onto dust: C + 4H -> CH4. However, most astrochemical models assume this reaction on the ice mantles of dust to be barrierless and efficient, without considering the states of adsorption. Recently, we found that C atoms exist in either the physisorbed or chemisorbed state on compact amorphous solid water, which is analogous to an interstellar ice mantle. These distinct adsorption states considerably affect the hydrogenation reactivity of the C atom. Herein, we elucidate the reactivities of physisorbed and chemisorbed C atoms with H atoms via sequential deposition and co-deposition processes. The results indicate that only physisorbed C atoms can produce CH4 on ice. Combining this finding with a previous estimate for the fraction of physisorbed C atoms on ice, we determined the upper limit for the conversion of C atoms into CH4 to be 30%.

astro-ph.GA↗

arXiv2024

Photodesorption efficiency of OH radical on the ice surface in the wavelength range from ultraviolet to visible

The photodesorption efficiencies of the hydroxyl (OH) radical from the water ice surface were measured in the range of 310-700 nm for the first time. Although isolated H$_2$O molecules and OH radicals do not absorb visible photons, the photodesorption of OH interacting with the ice surface was found to occur by a one-photon process in the entire visible range. The photodesorption efficiency strongly depended on the wavelength, and the analyses of photodesorption cross sections indicated that only strongly bound OH radicals were desorbed at longer wavelengths, whereas both weakly and strongly bound OH radicals were desorbed at shorter wavelengths.

physics.chem-ph↗

arXiv2023

Coverage Dependent H$_2$ Desorption Energy: a Quantitative Explanation Based on Encounter Desorption Mechanism

Recent experiments show that the desorption energy of H$_2$ on a diamond-like carbon (DLC) surface depends on the H$_2$ coverage of the surface. We aim to quantitatively explain the coverage dependent H$_2$ desorption energy measured by the experiments. We derive a math formula to calculate an effective H$_2$ desorption energy based on the encounter desorption mechanism. The effective H$_2$ desorption energy depends on two key parameters, the desorption energy of H$_2$ on H$_2$ substrate and the ratio of H$_2$ diffusion barrier to its desorption energy. The calculated effective H$_2$ desorption energy qualitatively agrees with the coverage dependent H$_2$ desorption energy measured by the experiments if the values of these two parameters in literature are used in the calculations. We argue that the difference between the effective H$_2$ desorption energy and the experimental results is due to the lacking of knowledge about these two parameters. So, we recalculate these two parameters based on experimental data. Good agreement between theoretical and experimental results can be achieved if these two updated parameters are used in the calculations.

astro-ph.GA↗

arXiv2023

Surface Diffusion of Carbon Atoms as a Driver of Interstellar Organic Chemistry

Many interstellar complex organic molecules (COMs) are believed to be produced on the surfaces of icy grains at low temperatures. Atomic carbon is considered responsible for the skeletal evolution processes, such as C-C bond formation, via insertion or addition reactions. Before reactions, C atoms must diffuse on the surface to encounter reaction partners; therefore, information on their diffusion process is critically important for evaluating the role of C atoms in the formation of COMs. In situ detection of C atoms on ice was achieved by a combination of photostimulated desorption and resonance enhanced multiphoton ionization methods. We found that C atoms weakly bound to the ice surface diffused approximately above 30 K and produced C2 molecules. The activation energy for C-atom surface diffusion was experimentally determined to be 88 meV (1,020 K), indicating that the diffusive reaction of C atoms is activated at approximately 22 K on interstellar ice. The facile diffusion of C at T > 22 K atoms on interstellar ice opens a previously overlooked chemical regime where the increase in complexity of COMs as driven by C atoms. Carbon addition chemistry can be an alternative source of chemical complexity in translucent clouds and protoplanetary disks with crucial implications in our current understanding on the origin and evolution of organic chemistry in our Universe.

astro-ph.GA↗

arXiv2022

Penetration of Non-energetic Hydrogen Atoms into Amorphous Solid Water and their Reaction with Embedded Benzene and Naphthalene

Chemical processes on the surface of icy grains play an important role in the chemical evolution in molecular clouds. In particular, reactions involving non-energetic hydrogen atoms accreted from the gaseous phase have been extensively studied. These reactions are believed to effectively proceed only on the surface of the icy grains; thus, molecules embedded in the ice mantle are not considered to react with hydrogen atoms. Recently, Tsuge et al. (2020) suggested that non-energetic hydrogen atoms can react with CO molecules even in ice mantles via diffusive hydrogenation. This investigation was extended to benzene and naphthalene molecules embedded in amorphous solid water (ASW) in the present study, which revealed that a portion of these molecules could be fully hydrogenated in astrophysical environments. The penetration depths of non-energetic hydrogen atoms into porous and non-porous ASW were determined using benzene molecules to be >50 and ~10 monolayers, respectively (1 monolayer ~ 0.3 nm).

astro-ph.GA↗

arXiv2021

Measurements of Ortho-to-para Nuclear Spin Conversion of H2 on Low-temperature Carbonaceous Grain Analogues: Diamond-like Carbon and Graphite

Hydrogen molecules have two nuclear spin isomers: ortho-H2 and para-H2. The ortho-to-para ratio (OPR) is known to affect chemical evolution as well as gas dynamics in space. Therefore, understanding the mechanism of OPR variation in astrophysical environments is important. In this work, the nuclear spin conversion (NSC) processes of H2 molecules on diamond-like carbon and graphite surfaces are investigated experimentally by employing temperature-programmed desorption and resonance-enhanced multiphoton ionization methods. For the diamond-like carbon surface, the NSC time constants were determined at temperatures of 10-18 K and from 3900 plusminus 800 s at 10 K to 750 plusminus 40 s at 18 K. Similar NSC time constants and temperature dependence were observed for a graphite surface, indicating that bonding motifs (sp3 or sp2 hybridization) have little effect on the NSC rates.

astro-ph.GA↗

arXiv2021

Transmission Electron Microscopy Study of the Morphology of Ices Composed of H2O, CO2, and CO on Refractory Grains

It has been implicitly assumed that ices on grains in molecular clouds and proto planetary disks are formed by homogeneous layers regardless of their composition or crystallinity. To verify this assumption, we observed the H2O deposition onto refractory substrates and the crystallization of amorphous ices (H2O, CO2, and CO) using an ultra-high-vacuum transmission electron microscope. In the H2O-deposition experiments, we found that three-dimensional islands of crystalline ice (Ic) were formed at temperatures above 130 K. The crystallization experiments showed that uniform thin films of amorphous CO and H2O became three-dimensional islands of polyhedral crystals; amorphous CO2, on the other hand, became a thin film of nano crystalline CO2 covering the amorphous H2O. Our observations show that crystal morphologies strongly depend not only on the ice composition, but also on the substrate. Using experimental data concerning the crystallinity of deposited ices and the crystallization timescale of amorphous ices, we illustrated the criteria for ice crystallinity in space and outlined the macroscopic morphology of icy grains in molecular clouds as follows: amorphous H2O covered the refractory grain uniformly, CO2 nano-crystals were embedded in the amorphous H2O, and a polyhedral CO crystal was attached to the amorphous H2O. Furthermore, a change in the grain morphology in a proto-planetary disk is shown. These results have important implications for the chemical evolution of molecules, non-thermal desorption, collision of icy grains, and sintering.

astro-ph.GA↗

arXiv2021

Behavior of Hydroxyl Radicals on Water Ice at Low Temperatures

Because chemical reactions on/in cosmic ice dust grains covered by amorphous solid water (ASW) play important roles in generating a variety of molecules, many experimental and theoretical studies have focused on the chemical processes occurring on the ASW surface. In laboratory experiments, conventional spectroscopic and mass-spectrometric detection of stable products is generally employed to deduce reaction channels and mechanisms. However, despite their importance, the details of chemical reactions involving reactive species (i.e., free radicals) have not been clarified because of the absence of experimental methods for in situ detection of radicals. Because OH radicals can be easily produced in interstellar conditions by not only the photolysis and/or ion bombardments of H2O but also the reaction of H and O atoms, they are thought to be one of the most abundant radicals on ice dust. In this context, the development of a close monitoring method of OH radicals on the ASW surface may help to elucidate the chemical reactions occurring on the ASW surface.

astro-ph.GA↗

arXiv2021

Rapid ortho-to-para nuclear spin conversion of H2 on a silicate dust surface

The H2 molecule has two nuclear spin isomers, the so-called ortho and para isomers. Nuclear spin conversion (NSC) between these states is forbidden in the gas phase. The energy difference between the lowest ortho and para states is as large as 14.7 meV, corresponding to ~170 K. Therefore, each state of H2 differently affects not only the chemistry but also the macroscopic gas dynamics in space, and thus, the ortho-to-para abundance ratio (OPR) of H2 has significant impacts on various astronomical phenomena. For a long time, the OPR of nascent H2 upon formation on dust grains has been assumed to have a statistical value of three and to gradually equilibrate in the gas phase at the temperature of the circumstances. Recently, NSC of H2 was experimentally revealed to occur on water ice at very low temperatures and thus incorporated into gas-dust chemical models. However, H2 molecules should form well before dust grains are coated by water ice. Information about how the OPR of H2 behaves on bare silicate dust before ice-mantle formation is lacking. Knowing the influence of the OPR of H2 if the OPR changes even on a bare silicate surface within an astronomically meaningful time scale is desirable. We report the first laboratory measurements of NSC of H2 physisorbed on amorphous silicate (Mg2SiO4) at temperatures up to 18 K. The conversion was found to occur very rapidly.

astro-ph.GA↗

arXiv2020

Diffusive hydrogenation reactions of CO embedded in amorphous solid water at elevated temperatures ~70 K

The surface processes on interstellar dust grains have an important role in the chemical evolution in molecular clouds. Hydrogenation reactions on ice surfaces have been extensively investigated and are known to proceed at low temperatures mostly below 20 K. In contrast, information about the chemical processes of molecules within an ice mantle is lacking. In this work, we investigated diffusive hydrogenation reactions of carbon monoxide (CO) embedded in amorphous solid water (ASW) as a model case and discovered that the hydrogenation of CO efficiently proceeds to yield H2CO and CH3OH even above 20 K when CO is buried beneath ASW. The experimental results suggest that hydrogen atoms diffuse through the cracks of ASW and have a sufficient residence time to react with embedded CO. The hydrogenation reactions occurred even at temperatures up to ~70 K. Cracks collapse at elevated temperatures but the occurrence of hydrogenation reactions means that the cracks would not completely disappear and remain large enough for penetration by hydrogen atoms. Considering the hydrogen-atom fluence in the laboratory and molecular clouds, we suggest that the penetration of hydrogen and its reactions within the ice mantle occur in astrophysical environments. Unified Astronomy

astro-ph.GA↗

arXiv2019

Interactions of Atomic and Molecular Hydrogen with a Diamond-like Carbon Surface: H2 Formation and Desorption

The interactions of atomic and molecular hydrogen with bare interstellar dust grain surfaces are important for understanding H2 formation at relatively high temperatures (>20 K). We investigate the diffusion of physisorbed H atoms and the desorption energetics of H2 molecules on an amorphous diamond-like carbon (DLC) surface. From temperature-programmed desorption experiments with a resonance-enhanced multiphoton ionization (REMPI) method for H2 detection, the H2 coverage-dependent activation energies for H2 desorption are determined. The activation energies decrease with increasing H2 coverage and are centered at 30 meV with a narrow distribution. Using a combination of photostimulated desorption and REMPI methods, the time variations of the surface number density of H2 following atomic and molecular hydrogen depositions are studied. From these measurements, we show that H2 formation on a DLC surface is quite efficient, even at 20 K. A significant kinetic isotope effect for H2 and D2 recombination reactions suggests that H-atom diffusion on a DLC surface is mediated by quantum mechanical tunneling. In astrophysically relevant conditions, H2 recombination due to physisorbed H-atoms is unlikely to occur at 20 K, suggesting that chemisorbed H atoms might play a role in H2 formation at relatively high temperatures.

astro-ph.GA↗