-
[show abstract]
[hide abstract]
ABSTRACT: The photodesorption of H(2)O in its vibrational ground state, and of OH radicals in their ground and first excited vibrational states, following 157 nm photoexcitation of amorphous solid water has been studied using molecular dynamics simulations and detected experimentally by resonance-enhanced multiphoton ionization techniques. There is good agreement between the simulated and measured energy distributions. In addition, signals of H(+) and OH(+) were detected in the experiments. These are inferred to originate from vibrationally excited H(2)O molecules that are ejected from the surface by two distinct mechanisms: a direct desorption mechanism and desorption induced by secondary recombination of photoproducts at the ice surface. This is the first reported experimental evidence of photodesorption of vibrationally excited H(2)O molecules from water ice.
Physical Chemistry Chemical Physics 09/2011; 13(35):15810-20. · 3.57 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We investigated the OH-related formation routes of two astrophysically important molecules, H(2)O and CO(2), under relatively warm astrophysical conditions. OH radicals, together with other neutral species such as H, O, H(2), and O(2), were produced in H(2)O microwave-discharge plasma and cooled to 100 K before being deposited on an Al substrate at 40-60 K. H(2)O formed at 40 and 50 K, but not at 60 K. Taking the experimental conditions into account, a possible route of H(2)O formation is via reactions involving OH + OH, which yield H(2)O(2) as the main reaction product. The present study is the first to show experimentally that surface reactions of two OH radicals can yield H(2)O at low temperatures. The products' branching ratio was 0.2 and 0.8 for H(2)O and H(2)O(2), respectively. When CO was co-deposited with neutral species that formed in the H(2)O plasma, CO(2) was formed at 40-60 K. H(2)CO(3) formed at 40 and 50 K. The present results may suggest that chemical reactions related to OH radicals are effective at yielding various molecules in relatively warm astrophysical environments, such as protostars.
Physical Chemistry Chemical Physics 07/2011; 13(35):15792-7. · 3.57 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Photodissociation of amorphous ice films of carbon dioxide and water co-adsorbed at 90 K was carried out at 157 nm using oxygen-16 and -18 isotopomers with a time-of-flight photofragment mass spectrometer. O((3)P(J)) atoms, OH (v = 0) radicals, and CO (v = 0,1) molecules were detected as photofragments. CO is produced directly from the photodissociation of CO(2). Two different adsorption states of CO(2), i.e., physisorbed CO(2) on the surface of amorphous solid water and trapped CO(2) in the pores of the film, are clearly distinguished by the translational and internal energy distributions of the CO molecules. The O atom and OH radical are produced from the photodissociation of H(2)O. Since the absorption cross section of CO(2) is smaller than that of H(2)O at 157 nm, the CO(2) surface abundance is relatively increased after prolonged photoirradiation of the mixed ice film, resulting in the formation of a heterogeneously layered structure in the mixed ice at low temperatures. Astrophysical implications are discussed.
Physical Chemistry Chemical Physics 06/2011; 13(35):15785-91. · 3.57 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We present the experimental results of carbonic acid (H2CO3) formation through surface reactions of CO molecules with non-energetic hydroxyl (OH) radicals at 10-40 K. The formation of H2CO3 was clearly identified both in the IR spectra and in the thermally programmed desorption mass spectra. The H2CO3 yield was rather high, amounting to approximately 40%-70% relative to that of CO2 formed by the reaction of CO with OH. The structure of H2CO3 formed by reactions of CO with OH may differ from that formed by energetic processes such as UV irradiation, ion irradiation, and electron irradiation of H2O/CO2 binary ices. In this paper, we envisage some of the possible roles H2CO3 may have in the interstellar medium, such as enriching grain mantles of new molecules via acid-base reactions with basic species and contributing to the formation of the unidentified band at 6.8 μm; we suggest possible reasons for its non-detection yet and discuss the restoration of carbonic acid molecules in the gas phase.
The Astrophysical Journal 09/2010; 722(2):1598. · 6.02 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Photodesorption of O(2)(X (3)Σ(g) (-)) and O(2)(a (1)Δ(g)) from amorphous solid water at 90 K has been studied following photoexcitation within the first absorption band at 157 nm. Time-of-flight and rotational spectra of O(2) reveal the translational and internal energy distributions, from which production mechanisms are deduced. Exothermic and endothermic reactions of OH+O((3)P) are proposed as plausible formation mechanisms for O(2)(X (3)Σ(g) (-) and a (1)Δ(g)). To examine the contribution of the O((3)P)+O((3)P) recombination reaction to the O(2) formation following 157 nm photolysis of amorphous solid water, O(2) products following 193 nm photodissociation of SO(2) adsorbed on amorphous solid water were also investigated.
The Journal of chemical physics 09/2010; 133(10):104504. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Physicochemical processes (H-atom sticking, diffusion, recombination, and the nuclear spin temperature of nascent H2 molecules) important in the formation of molecular hydrogen have been experimentally investigated on amorphous solid water (ASW). A new type of experiment is performed to shed light on a longstanding dispute. The diffusion rate of H atom is directly measured at 8 K and is found to consist of a fast and a slow component due to the presence of at least two types of potential sites with the energy depths of ~20 and >50 meV, respectively. The fast diffusion at the shallow sites enables efficient H2 formation on interstellar ice dust even at 8 K, while H atoms trapped in the deeper sites hardly migrate. The spin temperature of nascent H2 formed by recombination on ASW has been obtained for the first time and is higher than approximately 200 K. After formation, H2 molecules are trapped and their spin temperature decreases due to the conversion of spin states on ASW.
The Astrophysical Journal Letters 04/2010; 714(2):L233. · 5.53 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Following 157 nm photoexcitation of amorphous solid water and polycrystalline water ice, photodesorbed water molecules (H(2)O and D(2)O), in the ground vibrational state, have been observed using resonance-enhanced multiphoton ionization detection methods. Time-of-flight and rotationally resolved spectra of the photodesorbed water molecules were measured, and the kinetic and internal energy distributions were obtained. The measured energy distributions are in good accord with those predicted by classical molecular dynamics calculations for the kick-out mechanism of a water molecule from the ice surface by a hot hydrogen (deuterium) atom formed by photodissociation of a neighboring water molecule. Desorption of D(2)O following 193 nm photoirradiation of a D(2)O/H(2)S mixed ice was also investigated to provide further direct evidence for the operation of a kick-out mechanism.
The Journal of chemical physics 04/2010; 132(16):164508. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO2 was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO2 formation, due to reactions between CO and OH, occurs in tandem with H2O formation, and this may lead to the formation of CO2 ice in polar environments, as typically observed in molecular clouds.
The Astrophysical Journal Letters 03/2010; 712(2):L174. · 5.53 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Methanol is typically observed within water-rich interstellar ices and is a source of interstellar organic species. Following the 157 nm photoexcitation of solid methanol at 90 K, desorbed CH(3)(v=0) and OH(v=0,1) radicals have been observed in situ, near the solid surface, using resonance-enhanced multiphoton ionization (REMPI) detection methods. Time-of-flight and rotationally resolved REMPI spectra of the desorbed species were measured, and the respective fragment internal energy and kinetic energy distributions were obtained. Photoproduction mechanisms for CH(3) and OH radicals from solid methanol are discussed. The formation of O((1)D and (3)P) atoms and H(2)O was investigated, but the yield of these species was found to be negligible. CH(3) products arising following the photoexcitation of water-methanol mixed ice showed similar kinetic and internal energy distributions to those from neat methanol ice.
The Journal of chemical physics 12/2009; 131(22):224512. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Desorption of ground state O((3)P(J=2,1,0)) atoms following the vacuum ultraviolet photolysis of water ice in the first absorption band was directly measured with resonance-enhanced multiphoton ionization (REMPI) method. Based on their translational energy distributions and evolution behavior, two different formation mechanisms are proposed: One is exothermic recombination reaction of OH radicals, OH+OH-->H(2)O+O((3)P(J)) and the other is the photodissociation of OH radicals on the surface of amorphous solid water. The translational and internal energy distributions of OH radicals as well as the evolution behavior were also measured by REMPI to elucidate the roles of H(2)O(2) and OH in the O((3)P(J)) formation mechanisms.
The Journal of chemical physics 09/2009; 131(11):114511. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We have studied the desorption dynamics of OH radicals from the 157 nm photodissociation of amorphous solid water (ASW) as well as H(2)O(2) deposited on an ASW surface at 90 K. The translational and internal energy distributions of OH were measured using resonance-enhanced multiphoton ionization methods. These distributions are compared to reported molecular dynamics calculations for the condensed phase photodissociation of water ice and also reported results for the gas phase photodissociation of H(2)O at 157 nm. We have confirmed that OH radicals are produced from two different mechanisms: one from primary photolysis of surface H(2)O of ASW, and the other being secondary photolysis of H(2)O(2) photoproducts on the ASW surface after prolonged irradiation at 157 nm.
The Journal of chemical physics 09/2009; 131(5):054508. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Translationally and internally hot H(2) molecules are produced from the 157 nm photodissociation of amorphous solid methanol at 90 K by two distinct mechanisms: exothermic recombination of two H-atom photoproducts bound to the surface and unimolecular molecular elimination of H(2) from the photoexcited methanol. The vibrationally hot H(2)(v=2-5) products are characterized by high translational and rotational temperatures. A third mechanism, the almost thermoneutral abstraction of a hydrogen atom from methanol parent molecule by the photolytically produced hydrogen atom, yields translationally and rotationally cold H(2)(v=0 and 1) products. Comparison with the results of the vacuum ultraviolet photolysis of water ice is discussed. Production of translationally hot and cold hydrogen atoms is also confirmed.
The Journal of chemical physics 05/2009; 130(16):164505. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We demonstrate experimentally that photodissociation of amorphous solid water at 100 K results in formation of H2 molecules with an ortho/para ratio of gOPR = 3. Two distinct mechanisms can be identified: endothermic abstraction of a hydrogen atom from H2O by a photolytically produced H atom yields vibrationally cold H2 products, whereas exothermic recombination of two H-atom photoproducts yields translationally and internally hot H2. These results are in accord with predictions by molecular dynamics calculations and their astrophysical implications are discussed.
The Astrophysical Journal 12/2008; 682(1):L69. · 6.02 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Production of gaseous OH radicals in the 248-350 nm photoirradiation of NO3(-) doped on amorphous ice at 100 K was monitored directly by using resonance-enhanced multiphoton ionization. The translational energy distribution of the OH product was represented by a Maxwell-Boltzmann energy distribution with the translational temperature of 3250 +/- 250 K. The rotational temperature was estimated to be 175 +/- 25 K. We have confirmed that the OH production should be attributed to the secondary photolysis of H2O2 produced on ice surface on the basis of the results of controlled photolysis experiments for H2O2 doped on ice surface.
The Journal of Physical Chemistry A 10/2008; 112(40):9763-6. · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: The production of gaseous OH radicals from the 300-350 nm photodissociation of H(2)O(2) that was photolytically produced on a water ice surface following the 157 nm photolysis of water ice at 90 K was directly monitored using resonance-enhanced multiphoton ionization. The translational energy distribution estimated by the time-of-flight spectrum of the OH products is represented by a Maxwell-Boltzmann energy distribution with a translational temperature of 3750+/-250 K. The rotational temperature was estimated by a spectral simulation to be 225+/-25 K. Surface defects produced by HCl deposition on the water ice contributed to the higher production rate of H(2)O(2) in the 157 nm photoirradiation of water ice while surface coverage caused by CD(3)OH deposition decreased the H(2)O(2) production rate.
The Journal of chemical physics 08/2008; 129(1):014709. · 3.09 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: The production of H2 in highly excited vibrational and rotational states (v = 0–5, J = 0–17) from the 157 nm photodissociation of amorphous solid water ice films at 100 K was observed directly using resonance-enhanced multiphoton ionization. Weaker signals from H2(v = 2,3 and 4) were obtained from 157 nm photolysis of polycrystalline ice, but H2(v = 0 and 1) populations in this case were below the detection limit. The H2 products show two distinct formation mechanisms. Endothermic abstraction of a hydrogen atom from H2O by a photolytically produced H atom yields vibrationally cold H2 products, whereas exothermic recombination of two H-atom photoproducts yields H2 molecules with a highly excited vibrational distribution and non-Boltzmann rotational population distributions as has been predicted previously by both quantum-mechanical and molecular dynamics calculations.
The Journal of Chemical Physics 07/2008; 129(4):044501-044501-8. · 3.33 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Mixtures of water (H 2 O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm −1 (5.92 and 8.17 μm, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH +) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeled water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide–water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.
The Astrophysical Journal. 08/1925; 727.
-
[show abstract]
[hide abstract]
ABSTRACT: Water ice is the major solid component in a variety of astrophysical environments, e.g., cold and dense molecular clouds. Photodesorption plays a dominant role in consuming ice in such cold regions. In this study, photodesorption of vibrationally ground-state H2O(v = 0) from amorphous solid water has been investigated at 157 nm. Using a resonance-enhanced multiphoton ionization technique, the translational and rotational energy distributions of photodesorbed H2O(v = 0) were measured, i.e., Boltzmann distributions at 1800 and 300 K, respectively. These energies are in good accordance with those predicted by classical molecular calculations for water photodesorption due to a kick-out mechanism following absorption of a single photon; hot H atom released by photodissociation of H2O in ice transfers enough momentum to another H2O molecule to kick it off the surface. Desorption of D2O(v = 0) following 193 nm photoirradiation of a D2O/H2S mixed ice was investigated to provide further direct evidence for the operation of a kick-out mechanism. The other desorption mechanisms were also discussed in the context of possible photodesorption of vibrationally excited H2O.
Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 269(9):1011-1015. · 1.21 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Vacuum ultraviolet photolysis of water ice in the first absorption band was studied at 157 nm. Translational and internal energy distributions of the desorbed species, O(1D) and OH(ν = 0,1), were directly measured with resonance-enhanced multiphoton ionization method. Two different mechanisms are discussed for desorption of electronically excited O(1D) atoms from the ice surface. One is unimolecular dissociation of H2O to H2+O(1D) as a primary photoprocess. The other is the surface recombination reaction of hot OH radicals that are produced from photodissociation of hydrogen peroxide as a secondary photoprocess. H2O2 is one of the major photoproducts in the vacuum ultraviolet photolysis of water ice. © 2009 American Institute of Physics.
-
[show abstract]
[hide abstract]
ABSTRACT: Desorption of ground state O(3P_[J= 2,1,0]) atoms following the vacuum ultraviolet photolysis of water ice in the first absorption band was directly measured with resonance-enhanced multiphoton ionization (REMPI) method. Based on their translational energy distributions and evolution behavior, two different formation mechanisms are proposed: One is exothermic recombination reaction of OH radicals, OH+OH → H2O+O(3PJ) and the other is the photodissociation of OH radicals on the surface of amorphous solid water. The translational and internal energy distributions of OH radicals as well as the evolution behavior were also measured by REMPI to elucidate the roles of H2O2 and OH in the O(3PJ) formation mechanisms. © 2009 American Institute of Physics.
