T.
Suhasaria
*a,
J. D.
Thrower
a,
R.
Frigge†
ab,
S.
Roling
a,
M.
Bertin
c,
X.
Michaut
c,
J.-H.
Fillion
c and
H.
Zacharias
ad
aPhysikalisches Institut, Westfälische Wilhelms Universität, Wilhelm Klemm Straße 10, 48149 Münster, Germany. E-mail: john.thrower@uni-muenster.de; h.zacharias@uni-muenster.de
bCenter for Nanotechnology (CeNTech), Westfälische Wilhelms-Universität, 48149 Münster, Germany
cSorbonne Université, Observatoire de Paris, PSL Research University, Laboratoire d'Etudes du Rayonnement et de la Matière en Astrophysique et Atmosphères, CNRS UMR 8112, 75005 Paris, France
dCenter for Soft Nanoscience, Westfälische Wilhelms Universität, 48149, Münster, Germany
First published on 8th February 2018
The photochemical processing of a CH4:D2O 1:3.3 ice mixture adsorbed on an HOPG surface in the XUV regime was investigated using pulses obtained from the Free-electron LASer in Hamburg (FLASH) facility. Ice films were exposed to femtosecond pulses with a photon energy of hν = 40.8 eV, consistent with the HeII resonance line. Cationic species desorbing directly from the ice films were detected using time-of-flight (ToF) mass spectrometry. Simple ions formed through the fragmentation of the parent molecules and subsequent recombination reactions were detected and are consistent with efficient D+ and H+ ejection from the parent species, similar to the case for low energy electron irradiation. The FEL fluence dependencies of these ions are linear or exhibit a non-linear order of up to 3. In addition, a series of Cn+ cluster ions (with n up to 12) were also identified. These ions display a highly non-linear desorption yield with respect to the FEL fluence, having an order of 6–10, suggesting a complex multi-step process involving the primary products of CH4 fragmentation. Two-pulse correlation measurements were performed to gain further insight into the underlying reaction dynamics of the photo-chemical reactions. The yield of the D2O derived products displayed a different temporal behaviour with respect to the Cn+ ions, indicating the presence of very different reaction pathways to the two families of ionic products.
CH4 ice has been observed in a variety of sources in the ISM as discussed by Boogert et al.2 who compared the CH4 ice abundance relative to H2O for various sources. This study suggested an upper limit of <3% for quiescent dark cloud regions, and abundances between 0.4–1.6% for comets, 1–11% for low-mass young stellar objects (LYSOs) and values of 1–3% in massive young stellar objects (MYSOs). CH4 is believed to be formed through surface reactions on low temperature (∼15 K) grains and is thought to be typically embedded in a polar matrix such as H2O.14 Aside from the dominant carbon containing ice species, CO, which is implicated in the formation of CH3OH, CH4 is considered a starting point for the formation of complex organic molecules. Various laboratory experiments have been carried out to probe the non-thermal processing of pure CH415–21 and H2O:CH4 mixed ice.16,22–24 In both pure and mixed CH4 ices, the primary products were found to be simple hydrocarbons. Kaiser and Roessler15 demonstrated the formation of long chain alkanes, CxHx+2 with up to x = 14, through the exposure of pure CH4 ice to 9 MeV α particles and 7.3 MeV protons. In the presence of H2O, products such as CH3OH, formaldehyde (H2CO), CO, CO2 are also typically generated, while Moore and Hudson22 and Öberg et al.24 additionally found acetaldehyde (CH3CHO) and ethanol (C2H5OH).
Here we have extended our previous investigations of XUV processing of D2O ice to a mixed CH4:D2O ice, subsequently exposed to XUV photons at the HeII resonance line wavelength of λ = 30.4 nm (hν = 40.8 eV). Ionic photochemical products directly desorbed from the ice film were detected through time-of-flight (ToF) mass spectrometry, revealing simple ionic species attributed to fragmentation of the individual ice components, reaction products and a strong series of ionic carbon clusters Cn+ with n extending up to a value of at least 12. We additionally performed measurements of the laser fluence dependence of the ion desorption yields, complemented by two-pulse correlation measurements to gain further insight into the reactions occurring.
Under this assumption, for each component the exposure, in L, was converted to a surface coverage of Nads molecules cm−2 using the Hertz–Knudsen formula:
(1) |
Ice | Exposure L | Coverage molecules cm−2 | Coverage ML | Ice thickness nm |
---|---|---|---|---|
D2O | (27.4 ± 2.7) | (1.24 ± 0.11 × 1016) | (10.8 ± 1.1) | (6.3 ± 0.6) |
CH4 | (7.4 ± 0.7) | (3.74 ± 0.37 × 1015) | (5.7 ± 0.6) | (2.1 ± 0.2) |
XUV photon irradiation of the ice mixture was performed using pulsed radiation from the FLASH free electron laser.32 All irradiation experiments were performed with the sample at 15 K. A photon energy of hν = 40.8 eV (λ = 30.4 nm) corresponding to the HeII line was used. The FEL was operated in single bunch mode and at a repetition rate of 10 Hz. An average energy per pulse of (29.6 ± 7) μJ and an average pulse duration of ca. 80 fs were employed. -Polarized XUV photons were incident on the HOPG surface at an angle of θ = 67.5° to the surface normal. The beam was focussed by an ellipsoidal mirror with a focal length f = 2 m. The spatial profile, and hence the spot size of the beam at the sample position were determined using an X-ray CCD camera positioned at an equivalent focus position, to which the beam was directed by a moveable quartz plate. As a result of the oblique incidence angle, the beam produced an ellipsoidal spot with an area of (0.9 ± 0.1) × 10−3 cm2 yielding an average fluence of (32.9 ± 8) mJ cm−2 on the sample.
Ionic species desorbed directly during exposure of the ice film to the XUV radiation were selected according to their mass to charge ratio (m/z) using a Wiley-McLaren type linear time-of-flight (ToF) mass spectrometer. The ion signal on the micro channel plate of the ToF was monitored using a digital oscilloscope, gated and forwarded to the computer for storage. The corresponding pulse energy for each laser shot was stored and the mass spectra were generated by averaging over, typically, 1000 shots.
The use of femtosecond duration pulses allows an examination of the underlying ultrafast dynamics of the photochemical reactions through time-resolved measurements. For this purpose, the split-and-delay unit (SDU)33–35 was employed to split the incident XUV pulses into two temporally separated components. The SDU produces two identical jitter-free pump–probe pulses provided with a tuneable temporal separation of −2 to +6 ps. Siemer et al.13 previously performed similar measurements for elucidating the XUV photochemical reaction mechanisms in D2O ice. The spatial overlap of the two pulses, after recombination, was monitored using the X-ray CCD camera discussed above. The stability of the overlap was monitored over the entire delay range between the pump–probe beams. At the employed photon energy the SDU has a transmittance of 48%35 which is taken into account when determining the incident fluence.
n = n − ik = (1 − δ) − iβ | (2) |
Given that some of the incident beam is absorbed by the HOPG substrate, the extent to which the desorption of carbon cluster ions from the bare HOPG surface occurs needs to be considered. Fig. 1 shows the ion desorption spectrum obtained for XUV irradiation of the bare HOPG surface for two different incident fluences. Clearly, at an incident fluence of (78 ± 11) mJ cm−2, Cn+ clusters (up to n = 11) are ejected from the bare HOPG surface. However, as shown in the inset, the yield of Cn+ clusters is significantly reduced at an incident fluence of ca. (40 ± 10) mJ cm−2. It should be noted that in this case the SDU was not inserted into the beamline and significantly higher incident fluences were attainable at the sample. Thus, considering the lower incident fluence employed in the measurements performed with the adsorbed film and the reduced intensity reaching the ice–HOPG interface as a result of absorption by the ice film, we do not expect a significant cluster yield originating from the substrate.
In addition to these simple species, we observe a series of peaks centered around 28 amu which could be attributed to the C2 hydrocarbon species C2H3+, C2H4+, C2H5+, and C2H6+ with masses of 27, 28, 29 and 30, respectively. The increased intensity of 28 amu with respect to the others in this series points to an additional contribution from CO+ which, along with CO2+ observed at 44 amu, is consistent with the formation of neutral CO and CO2 resulting from the irradiation of CH4:H2O ices as observed at lower photon energies.23,24 The peak at 30 amu could also contain a contribution from H2CO+ while that at 32 amu could correspond to both O2+ and CH3OH+. However, the lack of a clearly observable signal at 33 amu corresponding to CH3OD+ would appear to rule out the latter. Finally, we note that the peak at 44 amu might also be attributed to acetaldehyde (CH3CHO+).
The most striking observation is the appearance of the additional family of broader desorption peaks separated by ca. 12 amu which appear to be shifted to non-integer mass values. Given the otherwise clear alignment of peaks with the mass scale, this does not appear to be related to the calibration of the ToF. Furthermore, there does not appear to be a consistent separation between adjacent peaks on the mass scale, rather the spacing increases with mass. It was found that by shifting the flight time by −80 ns all of the peaks in this family aligned to integer multiples of 12 amu, consistent with the desorption of a series of carbon clusters (Cn+) with n values of up to at least 12, noting that the mass range of the ToF mass spectrometer was around 150 amu. ToF mass spectra on a shot-to-shot basis revealed that the signals corresponding to the carbon cluster ions strongly depend on fluence, dominating the spectrum for individual pulses with a higher energy, while the simple ionic species were observed more consistently for all pulse energies. However, there is no clear evolution of the shot-to-shot mass spectra as a function of overall irradiation time. In order to gain more insight into this behaviour, the fluence dependence of the desorption signals was assessed.
Y ∼ IK | (3) |
While the simple ionic products tend to show fluence dependencies in the range 1 ≤ K ≤ 3, the desorption of Cn+ clusters exhibit highly non-linear dependencies on the FEL fluence. Fig. 4 shows the fluence dependencies for all of the carbon cluster ions detected with the exception of C12+ which displays a very small desorption signal. Values of K between 6 and 10 were obtained as shown in Fig. 4. At the highest fluences the desorption signal shows saturation for the Cn+ clusters, as seen in Fig. 4. However, for the simple ionic products the desorption signal even decreases by about an order of magnitude, as can be noticed in Fig. 3. Such a decrease in the desorption signal of the simple ions points to a change in the chemistry at the highest fluences. It may possibly be assigned to the further dissociation of the simple ions. Therefore, for the determination of K, the desorption signal at the highest fluences is not taken into account. Table 2 summarizes the masses of all detected ions and their possible assignments along with the value of K derived from the fluence dependence measurements.
Mass/amu | Possible ions | Non-linearity, K |
---|---|---|
1 | H+ | 1.0 ± 0.01 |
2 | D+/H2+ | 1.3 ± 0.1 |
3 | HD+ | 1.4 ± 0.1 |
4 | D2+ | 1.4 ± 0.1 |
12 | C+ | 8.5 ± 1.2 |
14 | CH2+ | 1.6 ± 0.1 |
15 | CH3+ | 2.0 ± 0.2 |
16 | CH4+/O+ | 2.3 ± 0.3 |
17 | OH+ | 2.3 ± 0.3 |
18 | OD+ | 2.5 ± 0.2 |
19 | HOD+ | 1.8 ± 0.5 |
20 | D2O+ | 1.9 ± 0.5 |
24 | C2+ | 7.9 ± 1.5 |
26 | C2H2+ | |
27 | C2H3+ | |
28 | CO+/C2H4+ | 1.3 ± 0.2 |
29 | C2H5+ | |
30 | C2H6+/H2CO+ | |
32 | O2+ | |
36 | C3+ | 8.7 ± 2.1 |
40 | C3H4+/(D2O)2+ | |
44 | CO2+/C3H8+/CH3CHO+ | |
48 | C4+ | 7.4 ± 0.8 |
60 | C5+ | 8.7 ± 1.6 |
72 | C6+ | 6.9 ± 0.6 |
84 | C7+ | 8.5 ± 1.6 |
96 | C8+ | 6.4 ± 1.6 |
108 | C9+ | 8.3 ± 2.2 |
120 | C10+ | 9.6 ± 1.3 |
132 | C11+ | 7.6 ± 0.4 |
144 | C12+ |
All of the Cn+ ions exhibit a maximum at Δt = 0 and a rapid reduction in intensity with increasing delay, as shown in Fig. 6. A Gaussian fit to the experimental correlation curve yields a full width at half maximum (FWHM) of ∼1.2 ps. The rise time value obtained above for ionic species which have contributions from the D2O molecule can be compared to the half width at half maximum of Gaussian fits to the correlation curves obtained for the carbon cluster ions. This comparison suggests a significantly shorter timescale for processes leading to the ejection of the carbon cluster ions compared to the D2O derived products. Interestingly, the two-pulse correlation measurements for the signal at 15 amu show a temporal behaviour strikingly similar to that observed for the carbon cluster ions. Compared to the other signals in this region of the mass spectrum, this mass can only be attributed to CH3+ while those at higher masses can also be attributed to oxygen containing species derived from D2O. A significant background is observed for CH3+ which further suggest an additional contribution due to a single photon process in the ejection of CH3+. The two-pulse correlation curves shown in Fig. 5 and 6 have an asymmetric peak shape which is most likely due to a slight difference in intensity between two partial beams delivered by the SDU.
We begin first by focussing on the observed ionic desorption products that can be attributed solely to the D2O component of the ice mixture. These ions include D+, D2+, O+, OD+, D2O+ and O2+. These ions were observed previously during the XUV irradiation of pure D2O ice13 and were described in terms of a reaction scheme involving first the dissociation of the D2O molecule and the ejection of D+ and OD+. The close to linear fluence dependence of the D+ signal at mass 2 suggests that a direct single photon process dominates the ejection of D+. Orlando et al.39 observed strong H+ electron stimulated desorption (ESD) from H2O which was attributed to the Coulomb explosion of 2-hole states, generated through the primary excitation event, with population of the dissociative 4a1 state driving the H+ desorption. The observed threshold was 22 eV, significantly lower than the photon energy employed in the present measurements. Such a mechanism for proton ejection was also associated with photon stimulated dissociation of the H2O molecule.40 It is reasonable that the same channel operates in the present case, giving rise to the observed linear fluence dependence. ESD measurements39 also indicated a single electron process with a threshold again at 22 eV for the desorption of H2+ which was attributed to a dissociative ionization involving direct molecular elimination. The observed yield of H2+ was ca. 50 times less than that of H+, similar to our observed D2+:D+ yield ratio of around 1:50, suggesting that a similar mechanism is likely involved.
The desorption of O+ and OD+ both show a non linear fluence dependence with K = 2.3 and 2.5, respectively, indicative of a process involving 2 photons, for example through the ionization and dissociation of the OD generated as a result of the primary D+ ejection. Similarly, a three-step process suggested previously13 involving D2O2, formed through OD recombination, acting as a reservoir species is also consistent with the observed fluence dependence of both O+ and OD+. Subsequent fragmentation of D2O2 provides energetically favorable pathways to many of the fragments observed.41 We note that in the present case, no direct observation of D2O2+ desorption was possible at 36 amu as this overlaps with the strong signal attributed to C3+. For pure D2O ice a non-linear dependence of K = 3 was observed for O2+ desorption while in the present case no clear dependence on the intensity of this peak with fluence was observed. The non-linear fluence dependence (K ≈ 2) observed for D2O+ suggests that a direct ejection is not the dominant mechanism, and that D+ is the dominant result of the primary excitation. Fragmentation of D2O241 provides a potential route toward D2O+, while (OD + D+) and (OD+ + D) provide alternative routes toward D2O+.42 Finally, we note the presence of signals at 3 and 17 amu which can be attributed to HD+ and OH+, respectively. The strong H+ signal dominates the ionic desorption spectrum, with a linear fluence dependence that suggests a simple single photon process that releases a proton which can then produce HD+ and OH+ through recombination reactions with other ion fragments.
The most striking feature in the ion desorption spectrum shown in Fig. 2 is the series of peaks separated by 12 amu that correspond to Cn+ ions. We observe ions with n values of up to 12, as limited by the range of our ToF mass spectrometer. The formation of neutral Cn clusters as a result of the VUV (λ = 120 nm) photolysis of solid methane has been observed recently by Lin et al.43 They exposed CH4 dispersed in solid neon at a molar ratio of 1:1000 to synchrotron radiation and observed, through infrared spectroscopy, the signatures of carbon clusters and hydrocarbon molecules. In the present case, as discussed above, the starting point for the carbon chemistry is likely the single photon ejection of a proton from the CH4 molecule. Dissociative auto ionization of CH4 has been observed in the gas phase through low energy electron excitation with a threshold of 22 eV44 and provides a viable route:
CH4 + hν → CH4* | (4) |
(5) |
Subsequent ionization and fragmentation of the CH3 radical could then account for the observed signals at 14 and 15 amu corresponding to CH2+ and CH3+, consistent with their non-linear fluence dependencies of K = 1.6 and 2.1, respectively. Either CH4+ or O+ could account for the observed signal at 16 amu, although as with the case of D2O+ which shows a rather small signal, O+ would appear to be the major contribution. This is supported by the temporal dependence obtained for this mass through the two-pulse correlation measurements which behaves in a similar way to the other D2O fragments.
In addition to ionic D2O fragments and the carbon cluster ions, we also observe a series of peaks centered around 28 amu. This mass region is consistent with the formation of C2 hydrocarbons of the general form C2Hy+ with (2 ≤ y ≤ 6), corresponding to the range 26–30 amu. The peak at 28 amu is clearly the strongest, and would correspond to C2H4+. It shows a near linear fluence dependence which is somewhat difficult to reconcile with a reaction mechanism that involves the initial fragmentation of two parent CH4 molecules. Unfortunately, the overlap between the peaks in this region precludes an assessment of the fluence dependence for the other masses.
We note that the formation of CO+ can also contribute to the signal at 28 amu, and similarly CO2+ to that at 44 amu, both of which are frequently observed during the energetic processing of mixed hydrocarbon and water ices.16,22–24 C3 hydrocarbons of the general formula C3Hz+ with (z = 4, 6, 8) might be expected to give another series of peaks above 36 amu although we only see clear peaks at 40 and 44 amu. Bossa et al.19 observed the formation of linear C2 and C3 hydrocarbons as a result of VUV irradiation of pure CH4 ice indicating that recombination of methane fragments within an ice film can provide a route toward larger hydrocarbons. Given the parent molecules present in the ice, CH3OD (or CH3OH) formation might also be expected although, as discussed above, the clear non-detection of the former at 33 amu would appear to rule this out, considering that CH3OD would be expected to form more readily from the primary fragments. Cruz-Diaz et al.45 also observed little CH3OH desorption during VUV irradiation of CH3OH ice, attributing this to fragmentation being the dominant channel, which in our case would return any methanol that is formed to the primary fragments. We note that we cannot rule out the presence of CH3OD, or indeed other solid state species such as hydrocarbons in the exposed ice column, as our experimental approach is sensitive only to ions that desorb directly from the ice.
Previous studies of the energetic processing of pure CH4 ice have focussed on those species that are retained in the solid state. For example, Bossa et al.19 used VUV photons, dominated by Lyman-α, to initiate photochemical reactions in pure CH4 ice. Species formed in the ice were subsequently thermally desorbed from the ice with a laser heating pulse with CHx (x = 1–3), C2Hy (y = 2, 4, 6) and C3Hz (z = 4, 6, 8) being identified. Similarly, ion irradiation of pure CH4 ice with 60 keV Ar2+,16 220 MeV16 O7+18 and 15.7 MeV16 O5+46 have been shown to result in the production of hydrocarbons including C2H2 (acetylene), C2H4 (ethylene), C2H6 (ethane), and C3H8 (propane) in the solid state as identified through infrared spectroscopy. The electron bombardment reaction of pure CH4 ice by 5 keV energetic electrons17 also resulted in the formation of CHx (x = 1–4) and C2Hy (y = 2–6) in the ice which was interpreted in terms of the sequential loss of mobile H atoms from CH4 and subsequent reactions between the radical species thus formed. It is therefore clear that similar reaction pathways are operative at the higher photon energy used in the present study and we cannot rule out the formation of these neutral species which are then retained in the solid state. Rather, in addition, ionization becomes important at higher photon energies, permitting the direct ejection of ionic species from the ice.
Similarly, for CH4:H2O mixed ice, previous ion16,22 and VUV photon irradiation23,24,47 measurements have been performed revealing the formation of a variety of species such as CO, CO2, H2CO, CH3OH, CH3CHO and CH3CH2OH. As with the pure CH4 derived species, we observe the ejection of some species that can be attributed to reactions between fragments originating from the two ice components. However, as discussed for the case of CH3OD, if any of these species are formed in the ice, subsequent destruction is dominant over ionization and ejection. We previously assigned the peak observed at 40 amu to (D2O)2+13 but the absence of the deuterated cluster (D2O)2D+ at 42 amu suggests otherwise. Propyne, C3H4, could also be a potential candidate for the signal observed at 40 amu.
The temporal behaviour of the desorption yields shows two distinct behaviours that allow us to separate the ionic desorption into two families. The species that correspond to ions that can be attributed directly to processes involving only the CH4 component of the ice, i.e. the Cn+ clusters and CH3+, show a desorption behaviour in which the desorption yield is peaked when the two partial beams are temporally overlapped. For longer delays between the two partial beams, the desorption yield falls rapidly such that the correlation curves show a FWHM of ca. 1.2 ps for Cn+. The form of the correlation curve for the CH4 derived species is consistent with the highly non-linear fluence dependencies associated with these ions. This suggests that their formation requires a significant input of energy within a short time in order to generate sufficient reactive fragments to form larger carbon containing species that can lead to the observed carbon cluster desorption. On the other hand, species that have a contribution from the D2O component of the ice display a contrasting behaviour, where a minimum in the desorption yield is observed when the partial beams are temporally overlapped, with the yield increasing for longer delays. To quantify this effect, a rise time of ca. 2 ps was evaluated from the temporal behaviour of the desorption signal of the species forming from either D2O alone or fragments of both of the parents. This can be compared to the half width at half maximum of the temporal response for the carbon cluster ions (0.6 ps). The timescale for the formation and desorption of the Cn+ clusters is therefore significantly shorter than that for the other species, which show a desorption signal that does not decrease even at the longest temporal delays possible with the SDU (6 ps). Previously, collisions between ion fragments were suggested as a possible reason for the longer desorption timescale for ionic species desorbing from pure D2O ice upon XUV irradiation,13 being consistent with the present observations. This effect can also be present here due to the involvement of an additional ice constituent, CH4, and the additional reaction pathways that lead to the carbon cluster ions. However, without further insight into the evolution of the condensed phase during irradiation this remains somewhat speculative.
In addition to the clear difference in the temporal behaviour of the two families of ions observed, there is also an apparent delay of ca. 80 ns for the Cn+ ions with respect to the other species. This might suggest the ejection of parent species that fragment at some later time yielding the observed cations. Lin et al.43 observed the formation of neutral carbon clusters Cn (n = 3–20), as well as simple hydrocarbons, resulting from the VUV photolysis of solid CH4 dispersed in neon at 3 K. Interestingly, the size distribution of the observed clusters shifted to higher n with an increasing degree of dilution and no Cn was observed from pure CH4. Raghavachari and Binkley48 performed ab initio calculations and studied the stabilities of small ionic carbon clusters Cn (n = 2–10). They showed that the odd-numbered Cn+ clusters (up to n = 7) are more stable than the even-numbered clusters. This study is consistent with the results obtained here which show that signal intensities of odd-numbered Cn+ clusters are larger than those of the even numbered Cn+.
Interestingly, no ion signal for methanol, a molecule of interstellar relevance in terms of the formation of more complex organic species, was observed as already discussed above. Similarly, rather than resulting in the significant desorption of hydrocarbon species, dehydrogenation appears to be important at these energies leading primarily to the ejection of bare carbon cluster ions. Monitoring of the solid state composition of the ice during irradiation would be necessary to confirm the presence of hydrocarbon species. Neutral carbon clusters are molecules of interstellar importance and have been suggested as a possible carrier of the diffuse interstellar bands (DIBs) and unidentified infrared (UIR) emission bands.49–51 The present investigation suggests that photon induced processing of hydrocarbon species at high photon energies might provide a route toward the production of such species. However, the strong non-linear fluence dependence observed would tend to limit their formation under interstellar conditions.
Fluence dependence measurements were performed for the detected ionic desorption products to provide further insight into the mechanisms of the underlying photochemical processes. The simple species tended to show a low order of non-linearity up to K = 3 consistent with reactions between fragments formed from the parent species present in the ice. On the other hand, the desorption signals for the carbon clusters show highly non-linear fluence dependencies of up to K > 9, suggesting that multiple reaction steps involving primary fragments are required to generate these larger species. A surprising observation is that although the C concentration in the ice mixture was smaller than the O abundance, an efficient carbon chemistry was observed. Rather than generating hydrocarbon species, including those containing functional groups such as OD from the D2O component of the ice, the higher energy photons appear to drive a chemistry dominated by the formation of bare carbon clusters. This is consistent with the strong H+ desorption signal which indicates that dehydrogenation is an important step in initiating the formation of the carbon species.
The two-pulse correlation measurements, performed using a split-and-delay unit, revealed that the simple ions can be attributed to the fragmentation of the D2O component of the ice. They showed an unexpected behaviour in which the desorption yield shows a minimum at Δt = 0 ps, corresponding to the temporal overlap of two pulses. The D2O derived ionic species show a longer timescale of ca. 2 ps estimated from the rise time of a Boltzmann sigmoidal fit to the desorption signal which increases as a function of delay time between the two partial beams. The behaviour is consistent with that observed previously for pure D2O ice13 and can similarly be attributed to collisions between the ionic fragments. On the other hand, the carbon cluster ions show a maximum at close to Δt = 0 ps. This suggests that the formation of the carbon cluster ions requires a significant input of energy on a short timescale, consistent with the need to activate multiple CH4 molecules in order to drive the complex multistep chemistry. This timescale for the Cn+ ionic species was estimated to be 1.2 ps as determined from the FWHM of a Gaussian fit to the correlation curve.
Footnotes |
† Present address: Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii, HI, 96822, USA. |
‡ For additional information see: http://henke.lbl.gov/optical_constants/ |
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