Of amorphous ice

Amorphous water (also called glassy water or amorphous ice) can form when the temperature is decreased extremely rapidly below the glass transition temperature (Tg) of water (about 130 K at 0.1 MPa) (Mishima and Stanley, 1998). There are three types of amorphous ice low-density amorphous ice (LDA), high-density amorphous ice (HDA), and very high-density amorphous ice (VHDA), with VHDA being discovered most recently (Finney et al., 2002). 

The low threshold energies for the production of D( S), 0( P), and 0( D2) show the importance of valence excited states in the BSD of neutral fragments [47]. The pathway for D( S) desorption probably involves D O D -I- OD. Ffowever, the thresholds for producing 0( P2) and 0( D2), which are the same within experimental error, are lower than the 9.5-and 11.5-eV thermodynamic energies required to produce 0( P2) + 2D( S) and 0( D2) + 2D( S), respectively. The low threshold values therefore indicate that the formation of 0( P2) and 0( D2) must occur by a pathway which involves simultaneous formation of D2. Kimmel et al. have in fact reported [46] a threshold for the production of D2 from D2O ice at — 6 to 7 eV, which supports this conclusion. Above the ionization threshold of amorphous ice, these excited states can be formed directly or via electron-ion recombination. 

Cometary activity occurring at great distance from the Sun (corresponding to temperatures <100 K) is probably controlled by ices more volatile than H20. For example, comet Hale-Bopp exhibited emission of highly volatile CO at great solar distances. Trapped CO was presumably released by crystallization of amorphous ice or sublimation of ice crystals at very low temperatures. 

In a given work computer simulations devoted to study of nanostructure of abovementioned cryogenic amorphous phases of ice, mechanisms of their transformations, and properties to accumulate methane and hydrogen was realized within the theoretical concepts thermo field dynamics [5] and quantum-field chemistry [6-9]. We developed two models of nanostructures corresponding to HDA-ice and LDA-ice, respectively. Some computations of energetic barriers locking molecules CH4 and H2 inside of amorphous ice were fulfilled. 

The question of whether there is a tme glassy nature of amorphous ices is of interest when speculating about possible liquid-liquid transitions in (deeply) supercooled water. For true glasses, the amorphous-amorphous transitions described here can be viewed as the low-temperature extension of liquid-liquid transitions among LDL, HDL, and possibly VHDL. That is, the first-order like LDA <-> HDA transition may map into a first-order LDL HDL transition, and the continuous HDA <-> VHDA transition may map into a smeared HDL VHDL transition. Many possible scenarios are used how to explain water s anomalies [40], which share the feature of a liquid-liquid transition [202, 207-212]. They differ, however, in the details of the nature of the liquid-liquid transition Is it continuous or discontinuous Does it end in a liquid-liquid critical point or at the reentrant gas-liquid spinodal ... 

Except for HGW, which is commonly accepted to be a true glass, there is a lot of debate and scientific discourse regarding a possible nanocrystalline nature of amorphous ices. Evidence is abundant in the literature both for a pro-glass and a contra-glass view. 

In Figure 11 we demonstrate the application of the contour CSM analysis on the lone-pair orbital of a distorted water molecule (perhaps a frozen moment of a vibration, or a water molecule in a matrix of amorphous ice, or a water molecule trapped in a micropore). The ratio of length of the two O-H bonds is 0.9 (instead... 

Chowdhury MR, Dore JC, Montague DC (1983) Neutron diffraction studies and CRN model of amorphous ice. J Phys Chem 87 4037 -4039... 

Tulk CA, Benmore CJ, Urquidi 1, King DD, Neuefeind 1, Tomberli B, Egelstaff PA. Structural studies of several distinct metastable forms of amorphous ice. Science 2002 297 1320-1323. 

The structural correlations are strongly enhanced in the under-cooled state as the temperature is reduced towaids the metastable limit of -40°C (to D2O) and various thermoph ical properties exhibit diverged behaviour [8]. The exact nature of this anomaly is still the subject of some controversy. However, the difiraction pattern indicates that the stmcture is evolving towards that of amorphous ice which is characterised as a continuous random networit of tetrahedral hydrogen-bonds [9]. Recent neutron measurements on amorphous ice [10] have re-infor the earlier conjectures tuid shown that the structure is similar to that of hyper-quenched glassy water produced by rapid cooling of micron-sized water droplets. It can now be realised that the CRN mo l for the disordered phase of ice is effectively the limiting stmcture of water at low temperatures. 

The issue of amorphous ice is an important one for comet activity and evolution (Bar-Nun et al., 1987 Gronkowski, 2002). It is widely mentioned in the literature, but there is some debate on whether it exists in comets. Keller and Jorda (2002) outlines several arguments that it should not occur in comets. He uses the work of... 

Kouchi A., Yamamoto T., Kozasa T., Kuroda T., and Greenberg J. M. (1994) Conditions for condensation and preservation of amorphous ice and crystallinity of astro-physical ices. Astron. Astrophys. 290, KX19-1018. 

Ip and Fernandes [ 101] calculated that 6x lO to 6x lO s g of cometry material could liave been delivered to Earth at the time of the formation of the great Oort Cloud of comets. This amount is equivalent to 4-40 times the present mass of the oceans, assuming about 50% of the cometaiy mass is ice. Owen and Bar-Nun [102] examined tlie ability of amorphous ice formed at temperatures below lOOK to trap ambient gases. By comparison of the compositions of gases trapped by ice with tlie compositions of the interstellar medium, comets, and planetary atmospheres, Owen and Bar-Nun [102] concluded that icy comets delivered a considerable fraction of the volatiles to the imier planets. Owen [83] emphasized that Uie potential supply of cometaiy materials is more than adequate. 

By comparing die observed spectra with spectra measured in die laboratory, one can determine the crystallinity of icy grains [3]. For Elias 16 (a molecular cloud), the observed feature around 3 pm fits die spectrum of amorphous ice at... 

---