Quantum chemical calculation on the potential energy surface of H2CO3 and its implication for martian chemistry

A detailed theoretical study of the potential energy surface of H₂CO₃ is explored at the CCSD(T)//B3LYP/aug-cc-pVTZ level. On the potential energy surface, 12 isomers of H₂CO₃ are located. Their molecular properties such as geometries, vibrational frequencies, rotational constants, dipole moments, gas-phase acidities, and relative energies are calculated. Various reaction pathways and decomposition products have also been discussed. Among these products, CO₂ and H₂O are definitely the most favorable products with predominant abundance. Large energy barriers are predicted for other dissociation channels leading to the formation of oxygen, formaldehyde, and so on. These high energy channels are not important thermodynamically and kinetically, but they might occur in the presence of cosmic rays in astronomic environments. From the present work we suggest that chemical reactions between CO₂ and H₂O at the polar ice caps could be a potential source of H₂CO and O₂, in addition to the previously proposed mechanisms, i.e., the oxidation of methane and cosmic-ray-mediated production through the intermediate H₂CO₃. The results of the present work may provide useful data to improve our understanding of icy chemistry at the polar caps on Mars.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

The radiolysis of SO2 and H2S in water ice: Implications for the icy jovian satellites

Spectra of Europa, Ganymede, and Callisto reveal surfaces dominated by frozen water, hydrated materials, and minor amounts of SO₂, CO₂, and H₂O₂. These icy moons undergo significant bombardment by jovian magnetospheric radiation (protons, electrons, and sulfur and oxygen ions) which alters their surface compositions. In order to understand radiation-induced changes on icy moons, we have measured the mid-infrared spectra of 0.8 MeV proton-irradiated SO₂, H₂S, and H₂O-ice mixtures containing either SO₂ or H₂S. Samples with H₂O/SO₂ or H₂O/H₂S ratios in the 3-30 range have been irradiated at 86, 110, and 132 K, and the radiation half-lives of SO₂ and H₂S have been determined. New radiation products include the H₂S₂ molecule and HSO⁻₃, HSO⁻₄, and SO²⁻₄ ions, all with spectral features that make them candidates for future laboratory work and, perhaps, astronomical observations. Spectra of both unirradiated and irradiated ices have been recorded as a function of temperature, to examine thermal stability and phase changes. The formation of hydrated sulfuric acid in irradiated ice mixtures has been observed, along with the thermal evolution of hydrates to form pure sulfuric acid. These laboratory studies provide fundamental information on likely processes affecting the outer icy shells of Europa, Ganymede, and Callisto.     

Structure of ices on satellites

Ices on satellites in the solar system undergo changes produced by meteoritic bombardment, pressure, and thermal effects. The effect of the meteoritic bombardment on (porous) ices is some densification, but mainly the formation of crystalline H₂O polymorphs and the establishment of a rough equilibrium ratio between hexagonal and amorphous forms below 150°K. As a result of the low temperatures, the pressure densification of porous ices is significant only at depths of at least hundreds of meters for large satellites. The densification process is controlled by creep, that is, by slow plastic deformation of the solid matrix for medium porosities and by diffusion for low porosities. The isothermal effect on porous ice is an extremely slow densification process caused by surface and volume diffusion. A thermal gradient leads to migration of pores toward the warmer end and, since the velocity of the pores is proportional to their size, to their clustering. As a result, smaller pores become eliminated and the pore size distribution changes. Quantitative analysis of these effects has been made for ices including the integrodifferential coagulation equation which gives the new pore size distribution and the steepening of the gradient of porosity. For CO₂-ice the rates of these effects can be estimated to be several orders of magnitude higher than for H₂O-ice. Various physical properties are significantly affected and, in particular, it is concluded that, on a time scale of 10⁸ to 10⁹ years, in satellites with a cold interior the outer icy layers may have become densified while the opposite is true when satellites such as Europa and perhaps Enceladus have an internal source of heat.     

The dust environment at Titan

To explain the observed abundances of CO₂ in Titan's atmosphere, a relatively high water deposition into the atmosphere needs to be invoked due to the importance of H₂O photolysis in CO₂ production. A likely source of H₂O is icy dust particles from space. This paper considers the direct dust input to Titan's atmosphere from the interplanetary environment, and also ejecta particles from micrometeoroid impacts with the icy satellites Hyperion, Iapetus and Phoebe. It is found that the likely mass influx to Titan is 10^–16 to 10^–15 kg m^–2 s^–1. This mass influx is an order of magnitude too low to explain the observed levels of CO₂ in Titan's atmosphere in the context of a recent photochemical model. This leads one to speculate as to the likelihood of one large impact to Titan in the recent past;i.e., that the atmosphere is not in equilibrium but is cnrrently losing CO₂.     

Vaporization in comets: The icy grain halo of comet west

The variation with heliocentric distance of the production rates of various species in Comet West (1975n=1976 VI) is explained with a cometary model consisting of a CO₂-dominated nucleus plus a halo of icy grains of H₂O or clathrate hydrate. We conclude that the parents of CN and C₃ are released primarily from the nucleus but that the parent of C₂ is released primarily from the halo of icy grains.     

CO/CO2 Molecular Number Ratio Produced by ion Irradiation of Ices

We have quantitatively studied, by infrared absorption spectroscopy, the CO/CO₂ molecular number ratio after ion irradiation of ices and mixtures containing astrophysically relevant species such as CO, CO₂, H₂O, CH₄, CH₃OH, NH₃, O₂, and N₂ at 12–15 K. The ratios have also been measured after warm up to temperatures between 12 and 200 K. As a general result we find that the CO/CO₂ ratio decreases with the irradiation dose (amount of energy deposited on the sample). In all of the studied mixtures, as expected, it decreases with increasing temperature because of CO sublimation. However the temperature where CO sublimes strongly depends on the initial mixture, remaining at a temperature over 100 K in some cases. Our results might be relevant to interpret the observed CO/CO₂ ratio in several astrophysical scenarios such as planetary icy surfaces and ice mantles on grains in the interstellar medium. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ammonia-water ice laboratory studies relevant to outer Solar System surfaces

Although water- and ammonia-ices have been observed or postulated as important components of the icy surfaces of planetary satellites in the outer Solar System, significant gaps exist in our knowledge of the spectra and behavior of such mixtures under astrophysical conditions. To that end, we have completed low-temperature spectroscopic studies (1-20 μm) of water-ammonia mixtures, with an emphasis on features in the near-IR, a region which is accessible to ground-based observations. The influences of composition, formation temperature, thermal- and radiation-processing, and phase (crystalline or amorphous) of the components were examined. Spectra of both pure NH₃ and H₂O-NH₃ icy mixtures with ratios from 0.7 to 57 were measured at temperatures from 10 to 120 K. Conditions for the formation and thermal stability of the ammonia hemihydrate (2NH₃⋅H₂O) and the ammonia monohydrate (NH₃⋅H₂O) have been examined. Band positions of NH₃ in different H₂O-ices and major band positions of the hydrates were measured. We report spectral shifts that depend on concentration and temperature. The radiation-induced amorphization of the hemihydrate was observed and the radiation destruction of NH₃ in H₂O-ices was measured. Implications of these results for the formation, stability, and detection of ammonia on outer satellite surfaces are discussed.     

A review of possible optical absorption features of oxygen molecules in the icy surfaces of outer solar system bodies

In this review we provide the data needed to interpret remote spectroscopic studies of O₂ molecules embedded in the icy surfaces of outer solar system bodies. O₂ produced by radiolysis has been seen in the gas phase and as the so-called ‘solid O₂’ trapped in the icy surfaces of Ganymede, Europa and Callisto. It may also have been indirectly observed on a number of objects by its radiolysis product, O₃. These observations indicate the importance of O₂ for understanding the chemical processes occurring on icy outer solar system surfaces. Therefore, the published absorption spectra of gaseous, liquid and solid O₂ and of O₂ embedded in H₂O ice are reviewed in some detail. Particular emphasis has been placed on the presentation of transition probabilities for the various O₂ spectral series so that their relative importances can be assessed when they are used for modelling the radiation chemistry occurring in such environments.     

Cratering of icy targets by different impactors: Laboratory experiments and implications for cratering in the Solar System

Studies of impacts (impactor velocity about 5 km s⁻¹) on icy targets were performed. The prime goal was to study the response of solid CO₂ targets to impacts and to find the differences between the results of impacts on CO₂ targets with those on H₂O ice targets. The crater dimensions in CO₂ ice were found to scale with impact energy, with little dependence on projectile density (which ranged from nylon to copper, i.e., 1150-8930 kg m⁻³). At equal temperatures, craters in CO₂ ice were the same diameter as those in water ice, but were shallower and smaller in volume. In addition, the shape of the radial profiles of the craters was found to depend strongly on the type of ice and to change with impact energy. The impact speed of the data is comparable to that for impacts on many types of icy bodies in the outer Solar System (e.g., the satellites of the giant planets, the cometary nuclei and the Kuiper Belt objects), but the size and thus energy of the impactors is lower. Scaling with impact energy is demonstrated for the impacts on CO₂ ice. The issue of impact disruption (rather than cratering) is discussed by analogy with that on water ice. Expressions for the critical energy density for the onset of disruption rather than cratering are established for water ice as a function of porosity and silicate content. Although the critical energy density for disruption of CO₂ ice is not established, it is argued that the critical energy to disrupt a CO₂ ice body will be greater than that for a (non-porous) water ice body of the similar mass.     

The structure of cometary atmospheres

The temperature distributions in cometary atmospheres at various heliocentric distances for comets of Bennett and Encke types have been calculated by taking into account heating due to the absorption of solar ultraviolet radiation, cooling by H₂O far infrared emission, and various dynamical processes (expansion, advection, and thermal conduction). The agreement of the results with the observations is in general satisfactory. The conversion of CH₄ and NH₃ to CO and N₂ through thermochemical reaction with H₂O is concluded to be impossible, since the temperature is too low at a heliocentric distance 1.5 AU where CO⁺ ions begin to be observable.     

Liquid water on Mars: An energy balance climate model for CO2/H2O atmospheres

Geologic evidence of the prior existence of liquid water on Mars suggests surface temperatures T_s were once considerably warmer than at present; and that such a condition may have arisen from a larger atmospheric greenhouse. Here we develop a simple climate model for a CO₂/H₂O Mars atmosphere including water vapor-longwave opacity feedback in the atmosphere and temperature-albedo feedback at surface icecaps, under the assumption that once the Martian surface pressure was p_s ≥ 1 atm CO₂. Longwave flux to space is computed as a function of T_s and p_s using band-absorption models for the effect of the 15-μm fundamental, and the 10- and 15-μm hot bands, of the CO₂ molecule; as well as the pure rotation bands and e continuum of H₂O. The derived global radiative balance predicts a global mean surface temperature of 283°K at 1 atm CO₂. When the emission model is coupled to a latitudinally resolved energy balance climate model, including the effect of poleward heat transfer by atmospheric baroclinic eddies, the solutions vary, depending on p_s. We considered two cases: (1) the present Mars (p_s ? 0.007 atm) with pressure-buffering by solid CO₂ icecaps, and limited poleward heat flux by the atmosphere; and (2) a hypothetical “hot Mars” (p_s ? 1.0 atm), whose much higher CO₂ amount augmented by H₂O evaporative feedback yields a theoretical T_s distribution with latitude admitting liquid water over 95% of the surface, water icecaps at the poles, and a diminished equator-to-pole temperature gradient relative to the present.     

Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO₂) at or near the nominal solid-phase laboratory wavelength of 4.2675 μm (2343.3 cm⁻¹), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO₂ absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO₂, CO₂ clathrates, ternary mixtures of CO₂ with other volatiles, implanted and adsorbed CO₂ in non-volatile materials, and ab initio theoretical calculations of CO₂ * nH₂O. At the wavelength resolution of VIMS, the CO₂ on Phoebe is indistinguishable from pure CO₂ ice (each molecule’s nearby neighbors are also CO₂) or type II clathrate of CO₂ in H₂O. In contrast, the CO₂ band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ∼4.255 μm (∼2350.2 cm⁻¹)) and broadened. These wavelengths are characteristic of complexes of CO₂ with different near-neighbor molecules that are encountered in other volatile mixtures such as with H₂O and CH₃OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe’s CO₂ is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO₂ on the other three satellites results at least in part from particle or UV irradiation of native H₂O plus a source of C, implantation or accretion from external sources, or redistribution of native CO₂ from the interior.The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 μm, apparently as a consequence of telluric CO₂ gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO₂ absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO₂ absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 μm centered on 4.28 μm. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO₂, as discussed in this paper.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

The Water-Ammonia Phase Diagram up to 300 MPa: Application to Icy Satellites

We performed high-pressure experiments on the crystallization of water ice I and III in the ammonia-water (NH₃)_x(H₂O)_(1−x) system, and apply the results to the interiors of icy bodies in the Solar System. Phase equilibrium lines between an entirely liquid solution and a liquid solution in which water ice forms (liquidus lines) were determined for ammonia concentration by mass X equal to 0.034, 0.0472, 0.111, 0.176, and 0.229. Growth-melting of ice I as well as ice III crystals were observed. Application of the results to icy satellites that are potential bearers of ammonia shows that ammonia admixture decreases the depth of the liquidus surface. A shift of the liquidus temperature within a satellite depends on three parameters: the ammonia concentration, X; the temperature gradient, α; and the product of density and gravity, ρg.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

The role of Fischer-Tropsch catalysis in the origin of methane-rich Titan

Fischer-Tropsch catalysis, which converts CO and H₂ into CH₄ on the surface of iron catalyst, has been proposed to produce the CH₄ on Titan during its formation process in a circum-planetary subnebula. However, Fischer-Tropsch reaction rate under the conditions of subnebula have not been measured quantitatively yet. In this study, we conduct laboratory experiments to determine CH₄ formation rate and also conduct theoretical calculation of clathrate formation to clarify the significance of Fischer-Tropsch catalysis in a subnebula. Our experimental result indicates that the range of conditions where Fischer-Tropsch catalysis proceeds efficiently is narrow (T∼500-600 K) in a subnebula because the catalysts are poisoned at temperatures above 600 K under the condition of subnebula (i.e., H₂/CO = 1000). This suggests that an entire subnebula may not become rich in CH₄ but rather that only limited region of a subnebula may enriched in CH₄ (i.e., CH₄-rich band formation). Our experimental result also suggests that both CO and CO₂ are converted into CH₄ within time significantly shorter than the lifetime of the solar nebula at the optimal temperatures around 550 K. The calculation result of clathration shows that CO₂-rich satellitesimals are formed in the catalytically inactive outer region of subnebula. In the catalytically active inner region, CH₄-rich satellitesimals are formed. The resulting CH₄-rich satellitesimals formed in this region play an important role in the origin of CH₄ on Titan. When our experimental data are applied to a high-pressure model for subnebula evolution, it would predict that there should be CO₂ underneath the Iapetus subsurface and no thick CO₂ ice layer on Titan's icy crust. Such surface and subsurface composition, which may be observed by Cassini-Huygens mission, would provide crucial information on the origin of icy satellites.     

Temperature effect on the photodissociation rates in the atmospheres of Mars and Venus

The available solar flux at a given altitude in the atmospheres of Mars and Venus is attenuated mainly by CO₂ (molecular absorption and Rayleigh scattering) with an extra contribution due to SO₂ on Venus. The dissociation cross section of CO₂ depends on temperature. At temperatures appropriate for these atmospheres (～250°K), the cross sections are about 15% lower than those at room conditions (Y.L. Yung and W.B. De More, 1982, Icarus, 51, 199). It is shown that this temperature effect cannot be neglected in the evaluation of photolysis rates. Calculations of the photodissociation coefficients of CO₂, SO₂, HCl, and H₂O are presented. For example, at the surface of Mars, the coefficient of H₂O is nearly multiplied by a factor of 10!     

A spectroscopic study of the surfaces of Saturn's large satellites: H2O ice, tholins, and minor constituents

We present spectra of Saturn's icy satellites Mimas, Enceladus, Tethys, Dione, Rhea, and Hyperion, 1.0-2.5 μm, with data extending to shorter (Mimas and Enceladus) and longer (Rhea and Dione) wavelengths for certain objects. The spectral resolution (R=λ/Δλ) of the data shown here is in the range 800-1000, depending on the specific instrument and configuration used; this is higher than the resolution (R=225 at 3 μm) afforded by the Visual-Infrared Mapping Spectrometer on the Cassini spacecraft. All of the spectra are dominated by water ice absorption bands and no other features are clearly identified. Spectra of all of these satellites show the characteristic signature of hexagonal H₂O ice at 1.65 μm. We model the leading hemisphere of Rhea in the wavelength range 0.3-3.6 μm with the Hapke and the Shkuratov radiative transfer codes and discuss the relative merits of the two approaches to fitting the spectrum. In calculations with both codes, the only components used are H₂O ice, which is the dominant constituent, and a small amount of tholin (Ice Tholin II). Tholin in small quantities (few percent, depending on the mixing mechanism) appears to be an essential component to give the basic red color of the satellite in the region 0.3-1.0 μm. The quantity and mode of mixing of tholin that can produce the intense coloration of Rhea and other icy satellites has bearing on its likely presence in many other icy bodies of the outer Solar System, both of high and low geometric albedos. Using the modeling codes, we also establish detection limits for the ices of CO₂ (a few weight percent, depending on particle size and mixing), CH₄ (same), and NH₄OH (0.5 weight percent) in our globally averaged spectra of Rhea's leading hemisphere. New laboratory spectral data for NH₄OH are presented for the purpose of detection on icy bodies. These limits for CO₂, CH₄, and NH₄OH on Rhea are also applicable to the other icy satellites for which spectra are presented here. The reflectance spectrum of Hyperion shows evidence for a broad, unidentified absorption band centered at 1.75 μm.