Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments

A phenomenon of termination of sputtering of protonated water clusters (H2O)nH⁺ in low-temperature secondary emission mass spectrometric studies of solid water was observed in the temperature range of crystallization of amorphous solid water (ASW). In this range the mass spectra contained only H₃O⁺,...

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Datum:2003
Hauptverfasser: Kosevich, M.V., Boryak, O.A., Shelkovsky, V.S., Orlov, V.V.
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Veröffentlicht: Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України 2003
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Zitieren:Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments / M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, V.V. Orlov // Физика низких температур. — 2003. — Т. 29, № 9-10. — С. 1061-1064. — Бібліогр.: 30 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-128931
record_format dspace
spelling Kosevich, M.V.
Boryak, O.A.
Shelkovsky, V.S.
Orlov, V.V.
2018-01-14T13:08:47Z
2018-01-14T13:08:47Z
2003
Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments / M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, V.V. Orlov // Физика низких температур. — 2003. — Т. 29, № 9-10. — С. 1061-1064. — Бібліогр.: 30 назв. — англ.
0132-6414
PACS: 68.49.Sf, 64.70.Kb, 61.43.-j, 36.40.Wa
https://nasplib.isofts.kiev.ua/handle/123456789/128931
A phenomenon of termination of sputtering of protonated water clusters (H2O)nH⁺ in low-temperature secondary emission mass spectrometric studies of solid water was observed in the temperature range of crystallization of amorphous solid water (ASW). In this range the mass spectra contained only H₃O⁺, H₂O⁺•, and OH⁺ ions. The following explanation of the revealed phenomenon is suggested: the heat supplied to the ASW sample by the bombarding particles is spent on initiation of an amorphous–crystalline transition within the condensed sample but not for the transfer of the sample matter to the gas phase. At the same time heat released on crystallization causes a local rise in temperature of the crystallizing sample surface, which enhances the rate of sublimation of ice. The resulting increased concentration of subliming water molecules over the sample surface is reflected in the growth of abundance of H₂O⁺• molecular ion-radical, produced by gas-phase ionization mechanism. The appearance of a set of low-mass peaks in the course of crystallization observed for some types of ASW samples is explained by the release of gases trapped in the ASW film during its growth.
This work was partially supported by the grant INTAS-99-00478.
en
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
Физика низких температур
Biological Systems at Low Temperatures
Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
spellingShingle Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
Kosevich, M.V.
Boryak, O.A.
Shelkovsky, V.S.
Orlov, V.V.
Biological Systems at Low Temperatures
title_short Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
title_full Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
title_fullStr Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
title_full_unstemmed Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
title_sort observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments
author Kosevich, M.V.
Boryak, O.A.
Shelkovsky, V.S.
Orlov, V.V.
author_facet Kosevich, M.V.
Boryak, O.A.
Shelkovsky, V.S.
Orlov, V.V.
topic Biological Systems at Low Temperatures
topic_facet Biological Systems at Low Temperatures
publishDate 2003
language English
container_title Физика низких температур
publisher Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
format Article
description A phenomenon of termination of sputtering of protonated water clusters (H2O)nH⁺ in low-temperature secondary emission mass spectrometric studies of solid water was observed in the temperature range of crystallization of amorphous solid water (ASW). In this range the mass spectra contained only H₃O⁺, H₂O⁺•, and OH⁺ ions. The following explanation of the revealed phenomenon is suggested: the heat supplied to the ASW sample by the bombarding particles is spent on initiation of an amorphous–crystalline transition within the condensed sample but not for the transfer of the sample matter to the gas phase. At the same time heat released on crystallization causes a local rise in temperature of the crystallizing sample surface, which enhances the rate of sublimation of ice. The resulting increased concentration of subliming water molecules over the sample surface is reflected in the growth of abundance of H₂O⁺• molecular ion-radical, produced by gas-phase ionization mechanism. The appearance of a set of low-mass peaks in the course of crystallization observed for some types of ASW samples is explained by the release of gases trapped in the ASW film during its growth.
issn 0132-6414
url https://nasplib.isofts.kiev.ua/handle/123456789/128931
citation_txt Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments / M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, V.V. Orlov // Физика низких температур. — 2003. — Т. 29, № 9-10. — С. 1061-1064. — Бібліогр.: 30 назв. — англ.
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AT shelkovskyvs observationofcrystallizationofamorphoussolidwaterundertheconditionsofsecondaryemissionmassspectrometricexperiments
AT orlovvv observationofcrystallizationofamorphoussolidwaterundertheconditionsofsecondaryemissionmassspectrometricexperiments
first_indexed 2025-11-26T01:42:50Z
last_indexed 2025-11-26T01:42:50Z
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fulltext Fizika Nizkikh Temperatur, 2003, v. 29, Nos. 9/10, p. 1061–1064 Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, and V.V. Orlov B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, 47 Lenin Ave., Kharkov 61103, Ukraine E-mail: mvkosevich@ilt.kharkov.ua A phenomenon of termination of sputtering of protonated water clusters (H2O)nH + in low-tem- perature secondary emission mass spectrometric studies of solid water was observed in the tempera- ture range of crystallization of amorphous solid water (ASW). In this range the mass spectra con- tained only H3O +, H2O +�, and OH+ ions. The following explanation of the revealed phenomenon is suggested: the heat supplied to the ASW sample by the bombarding particles is spent on initia- tion of an amorphous–crystalline transition within the condensed sample but not for the transfer of the sample matter to the gas phase. At the same time heat released on crystallization causes a lo- cal rise in temperature of the crystallizing sample surface, which enhances the rate of sublimation of ice. The resulting increased concentration of subliming water molecules over the sample surface is reflected in the growth of abundance of H2O +� molecular ion-radical, produced by gas-phase ion- ization mechanism. The appearance of a set of low-mass peaks in the course of crystallization ob- served for some types of ASW samples is explained by the release of gases trapped in the ASW film during its growth. PACS: 68.49.Sf, 64.70.Kb, 61.43.–j, 36.40.Wa 1. Introduction Investigations of solid water by means of secondary emission mass spectrometry [1–14] have used either amorphous solid water (ASW) obtained by vapor de- position on some surface cooled below the temperature of the glass transition of water Tg = 136 K [15–17] or crystalline ice. Under bombardment by energetic par- ticles — by neutral atoms of Aro or Xeo in a fast atom bombardment (FAB) mode, or ions of Cs+or Ar+ in secondary ion mass spectrometry (SIMS), with the energy varied in the 5–30 keV range — sets of protonated water clusters (H2O)nH + with n up to 30–50 are sputtered both from ASW and crystalline ice. The distribution of clusters in the secondary emis- sion mass spectra of the both forms of water is qualita- tively very similar, with a slight quantitative dif- ference in the abundances of some clusters. The measurements were usually conducted at some con- stant temperature. Secondary emission mass spectro- metric experiments were not performed, however, on gradual variation of the sample temperature in the range around the temperature of crystallization of ASW, which, according to the data of Ref.15, can start at 140–160 K and proceed in some temperature range up to 166 K. It was revealed in our previous works on LT FAB and SIMS of a number of organic and inorganic com- pounds that phase transitions in the sample matter are reflected in characteristic changes in cluster patterns of the secondary emission mass spectra [13, 14, 18–20]. The aim of the present work was to obtain second- ary emission mass spectra of vapor-deposited solid wa- ter in the temperature range of crystallization of ASW with the expectation of observing and investigating changes in the mass spectral pattern resulting from this type of transition. 2. Low-temperature secondary emission mass spectrometric experiments Mass spectrometric experiments were performed us- ing the magnetic sector mass spectrometer MI-1201E (Sumy, Ukraine) equipped with primary FAB ion source for generating a bombarding beam of argon at- © M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, and V.V. Orlov, 2003 oms; the energy of the primary ion beam before neu- tralization was 4–5 keV. The secondary ion source contained a cryogenic unit described in detail else- where [12]. The cryogenic unit, cooled by liquid ni- trogen, had a recess for a removable copper sample holder which could be cooled either externally or di- rectly in the ion source. A thermistor inserted into the unit served for temperature measurements. The cryo- genic unit was surrounded by a toroidal cryogenic shield cooled by liquid nitrogen, which provided effi- cient adsorption of residual gases inside the ion source. The pressure in the FAB secondary ion source ahead of the bombarding argon inlet was about 10–6 Pa. Polycrystalline ice samples were produced by freez- ing of deionized water in vapors of liquid nitrogen. Layers of ASW were produced in two ways. Vapors of water were deposited onto the substrate pre-cooled to the liquid nitrogen temperature from residual gases in the evacuation chamber of the direct sample inlet sys- tem. During the deposition the temperature of the sample holder did not rise above the one recommended for the procedure 140 K [15], which was controlled by direct temperature measurement after the insertion of the sample holder to the cryogenic block. Alterna- tively, water vapor was deposited on the cold sample holder directly in the secondary ion source. The source of low-pressure flux of water molecules was crystal- line hydrate CuSO4·5H2O kept in a heated ceramic ampoule near the sample holder. Substrates for ASW deposition were the bare copper sample holder, frozen crystalline H2O and D2O, and frozen solutions of in- organic salts. 3. Results and discussion In the FAB mass spectra of layers of ASW depos- ited by various methods on various substrates, as described in the Experimental Section, a set of protonated water clusters (H2O)nH + (n = 1–10) was present (Fig. 1,a). The spectral pattern, that is the types of clusters and distribution of their abundances, did not undergo any substantial changes on tempera- ture variation in the 77–140 K temperature range. On warming the sample up to 140–150 K a rather unex- pected and pronounced effect was observed: all cluster ions of water (H2O)nH + except for those with n = 1 (that is H3O +) decreased in abundance rather rapidly (during one spectrum scan) and disappeared from the spectrum. At the same time the absolute intensity of a peak at m/z 18 which can be attributed to water radi- cal-cation H2O +� increased by one to two orders of magnitude (Fig. 1,b). The intensity of a peak of the ion at m/z 17, which is known to be an OH+ fragment of H2O +�, increased similarly to that of its parent ion. Thus, the FAB mass spectrum contained only three in- tense peaks of H3O +, H2O +�, OH+ (Fig. 1,b). For some types of samples at somewhat higher tempera- tures of about 150–160 K a noisy spectrum with a peak at every mass started to interfere with the above three peaks in the low-mass range. It lasted for some time and then vanished, giving way to a recovered normal spectrum of ice containing a (H2O)nH + cluster set at temperatures of about 160–170K . The latter, in turn, after completion of rather rapid sublimation of the crystallized ice layer on further warming was replaced by the spectrum characteristic of an un- der-layer (substrate). Once happened on warming, the described transformations were not repeated on subsequent cyclic cooling-warming of the ice formed. The reported changes of mass spectra were qualita- tively reproducible with slight quantitative variations in several tens of independent experiments. The most remarkable feature of these changes is a temporary termination of production of all the ions except H3O + and H2O +� when a solid water sample is still definitely present on the sample holder. Even in 1062 Fizika Nizkikh Temperatur, 2003, v. 29, Nos. 9/10 M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, and V.V. Orlov Fig. 1. FAB mass spectra of solid water: spectral pattern of ASW, characteristic in the temperature range 77–110 K (a); peaks corresponding to protonated water clusters in the set (H2O)nH + (n = 1–10) are marked by ✽; (the unmarked pe- ak at m/z 30 corresponds to NO adsorbed from the residual gas at T < 110 K); mass spectrum recorded at � 150 K (b). the case of complete exhaustion of the water layer the spectra of the exposed under-layer should appear, but they did not. To explain the phenomena observed, the answers to at least two questions are to be searched for: what are the reasons for termination of the production of (H2O)nH + clusters with n > 1 and continuation of the production of the H3O + ion, and what is the origin of the abundant H2O +� ion. First of all, it is obvious that the temperature range of anomalous changes in the mass spectra is very close to the temperature range of spontaneous crystallization of ASW, which, according to the results of the relevant studies [15], can start on slow warming at 140–160 K and be completed at 166 K. The action of some external factors, including energetic particle impact, initiates the so-called explo- sive crystallization, which can start at 15 K lower than the spontaneous crystallization [15]. This allows us to suggest that any effect observed in this tempera- ture range may be connected with an amorphous–crys- talline transition in the sample. It is generally recognized that excitation caused by a bombarding particle in a condensed sample is ultimately converted to thermal energy [21]. It is known also that all heat deposited in a system in the phase transition state is consumed on carrying out the transition to its completion. In this light, it may be suggested that in the present experiments practically all the energy supplied by a bombarding particle to an ASW sample at 140–166 K is spent on performing the amorphous–crystalline transition. In the zone heated by a bombarding particle water molecules in the amor- phous layer acquire some degrees of freedom which al- lows them to rearrange in a regular crystalline struc- ture. Thus, heat is spent on initiation and support of the crystallization process within the condensed sam- ple but not for evaporation (sublimation) of molecules to the gas phase. This can explain the absence of «sputtering» of sample matter to the gas phase (the latter usually being revealed by registering charged water clusters). The effects described are valid both for spontaneous and particle-initiated scenarios of crystallization. The low flux of bombarding particles used in FAB experiments provides incidence of parti- cles to the surface areas undamaged by preceding im- pacts for at least 5 minutes, which means that the probability of a new particle impact to the zone crys- tallized after a previous particle impact (from which cluster sputtering becomes possible) is rather low in the time frame of the experiment. Concerning the origin of H3O + ions under the above described conditions, it is known that the very first event on contact of a bombarding particle with the condensed sample surface can consist in direct mechanical knock-out by direct momentum transfer or by recoil atoms of one or a few surface atoms or mole- cules, either in the neutral or charged forms [22–24]. The H3O + ion can be produced by this surface mecha- nism, which is independent of further events caused by the bombarding particle in the bulk sample [25]. The difference in the origin of the H3O + ion and (H2O)nH + clusters with n > 1 is supported by the re- sults of early experiments on the determination of the kinetic energy of the sputtered species, which appeared to be higher for H3O + in comparison with larger water cluster ions [2]. This mechanism, however, could not be responsible for the appearance of the abundant molecular radical ion H2O +�, since its abundance in ordinary secondary ion emission mass spectra of both ASW and crystalline ice is relatively small. The appearance of H2O +� is usually conditioned by the increase of water concen- tration in the gas phase over the sample surface [7], since it was proved that H2O +� ion is formed by the so-called gas-phase FAB mechanism [7,26]. The in- crease of absolute and relative intensity of the peak corresponding to H2O +� in the FAB mass spectra of ice was observed earlier [13,14,25] under conditions of high-rate sublimation of ice samples at a tempera- ture of about 200–220 K [27] preceding complete rapid exhaustion of the sample. This suggests that in the experiments under discussion (Fig. 1,b) the con- centration of water molecules in the gas phase be- comes relatively high apparently for the same reason, that is, due to active sublimation. Although the tem- perature of the sample holder and bulk sample is kept rather low (140–160 K), the temperature of the sam- ple surface can become noticeably higher due to the known thermal effect characteristic of ASW crystalli- zation. It was found earlier that the heat released on rapid crystallization can cause a rise in the tempera- ture of the sample surface in the crystallizing region of about 60–80 K [15]. Assuming that the starting tem- perature of the sample is above 140 K, its increase by 60–80 K will raise the local temperature to a value of 200–220 K, at which the rate of sublimation is high and sufficient for recording abundant H2O +� ions. As to the temporary appearance of a noisy spec- trum, this effect can be explained by ionization of gaseous species trapped within ASW on its deposition and released on its structural rearrangement during crystallization [17,28]. Some data on ASW deposition show that the amount of gases trapped by ASW can exceed by a factor of three the weight of the ASW sample [29]. The intense release of gases at a certain stage of ASW crystallization has been named the «mo- lecular volcano» effect [30]. Observation of crystallization of amorphous solid water under the conditions of secondary emission Fizika Nizkikh Temperatur, 2003, v. 29, Nos. 9/10 1063 Thus, the chain of events leading to the changes in the spectra presented in Fig. 1 can be summarized as follows. In the temperature range of ASW crystalliza- tion the energy deposited by a bombarding particle contributes to carrying out the crystallization. This al- ternative channel of heat dissipation prevents transfer of the sample matter to the gas phase on the interac- tion of the bombarding particle with the sample. Only relatively simple H3O + species are released by direct sputtering from the surface. Upon both spontaneous and initiated crystallization the latent heat of crystal- lization is released and the temperature of the sample surface rises to values at which the sublimation rate is rather high and provides a concentration of water va- por over the sample surface sufficient for abundant production of H2O +� by gas-phase FAB ionization. The effects described should be taken into account in the models of the interaction of accelerated parti- cles with amorphous ices in outer space [11]. 3. Conclusions In FAB mass spectrometric studies of solid water in the temperature range of ASW crystallization a phe- nomenon of the termination of sputtering of clusters (H2O)nH +, which are always the main constituents of mass spectra of both amorphous solid and crystalline water, was revealed. The spectra contained only H3O +, H2O +� and OH+ ions. An explanation of the observed phenomenon is suggested: the heat supplied to the sample by the bombarding particles is spent on carrying out the amorphous–crystalline transition but not for the transfer of the sample matter to the gas phase. At the same time heat released on crystalliza- tion causes a rise of the sample surface temperature, which enhances ice sublimation. The increased con- centration of subliming water over the sample surface is reflected in the increase of the abundance of the H2O +� molecular ion-radical, produced by gas-phase ionization. Acknowledgment. This work was partially supported by the grant INTAS-99-00478 . 1. G.D. Tantsyrev and E.N. Nikolaev, Pis’ma Zh. Eksp. Teor. Fiz. 13, 473 (1971) (in Russian). 2. G.D. Tantsyrev and E.N. Nikolaev, Dok. Akad. Nauk SSSR 206, 151 (1972) (in Russian). 3. E.N. Nikolaev and G.D. Tantsyrev, Zh. Tekh. Fiz. 45, 400 (1975) (in Russian). 4. E.N. Nikolaev, G.D. Tantsyrev, and V.A. Saraev, Zh. Tekh. 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Cherepin, Secondary Ion Mass Spectroscopy of Solid Surfaces, Science Press, Utrecht (1987). 25. M.V. Kosevich, O.A. Boryak, I.O. Stepanov, and V.S. Shelkovsky, Eur. Mass Spectrom. 3, 11 (1997). 26. M. Takayama, Int. J. Mass Spectrom. Ion Proc. 152, 1 (1996). 27. B.I. Verkin, V.F. Getmanets, and R.S. Mikhalchenko, Thermophysics of Low Temperature Sublimational Co- oling, Nauk. Dumka, Kiev (1980). 28. Water. A Comprehensive Treatise, Water and aqueous solutions at subzero temperatures, F. Frank (ed.), Vol. 7, Plenum Press, New York (1982). 29. F.A. Bar-Nun, J. Dror, E. Kochavi, and D. Laufer, Phys. Rev. B35, 2427 (1987). 30. R.S. Smith, C. Huang, E.K.L. Wong, and B.D. Kay, Phys. Rev. Lett. 79, 909 (1997). 1064 Fizika Nizkikh Temperatur, 2003, v. 29, Nos. 9/10 M.V. Kosevich, O.A. Boryak, V.S. Shelkovsky, and V.V. Orlov