Mechanisms of Electron-Induced Chemistry in Molecular Ices
Abstract
:1. Introduction
- (i)
- provides a summary of our experimental approach which relies on a sufficient resolution in electron energy to identify resonant enhancements and energetic thresholds in the energy dependence of product yields and thus the electron-molecule interactions that initiate product formation,
- (ii)
- shows how information on the mechanisms of electron-driven chemistry in ices can be obtained by investigating the energy dependence of several products in the same sample or by comparing different ice systems, and
- (iii)
- discusses that the chemistry following the initial electron-molecule encounter can be understood based on established reaction mechanisms known from organic chemistry combined with quantum chemical calculations.
2. Experimental Approach
- (i)
- Products that are formed after electron irradiation are identified from TDS data for characteristic m/z values. In the ideal case, the desorption of a particular species can be seen in TDS curves for several m/z values and the intensity of the desorption peaks for these different m/z reflects the intensities in the mass spectra (MS) of this compound recorded on the same instrument when leaking the pure vapor of the product into the UHV chamber.
- (ii)
- Product formation is quantified from integrated desorption signals for a characteristic m/z ratio. The absolute product yields can be derived by comparing these integrated desorption signals to those obtained from ices that have been prepared with defined composition and surface coverage, as can be deduced from TDS, so that the amount of the respective product is known [31,35,36]. Relative amounts of different products can also be obtained without such a standard sample by using partial ionization cross sections for the characteristic m/z ratios used to monitor the products. The partial ionization cross sections for a given m/z ratio with intensity of a specific product is defined by , where are the intensities of all m/z ratios of that product and is its total ionization cross section. These cross sections, that refer to the electron energy applied for ionization in the mass spectrometer, define the intensities with which specific m/z ratios appear in the mass spectrum. If known, they can be used as correction factor that is applied to compare the intensities for specific m/z ratios and thus also the desorption peak areas of two different products and to convert them to a relative yield [24,29,31].
- (iii)
- The thus obtained product yields are determined as function of electron exposure, which is defined as the transmitted charge per surface area as measured on the metal foil, to establish over which range they increase linearly with exposure. In this linear regime, the decay of the initial reactants is still negligible and the product is not yet consumed by electron irradiation [24,26,29,30,31,32,35,36]. Under this condition, the rate with which a product is formed is directly proportional to the applied electron exposure. This is the basis on which the rates of formation can be compared between different products.
- (iv)
- Product yields are then measured as function of electron energy (E0) for an exposure that is within the linear regime for all investigated electron energies. The energy dependence of the product yields gives information on the electron-molecule interactions that initiate product formation. This includes thresholds for electronic excitation or ionization as well as maxima within specific energy ranges that point to a contribution of electron attachment. These processes are summarized in Section 3. When monitoring product formation in mixed ices, it is not obvious from the energy dependence alone which constituent undergoes the initiating electron-molecule interaction if both show similar DI or ND thresholds or energy ranges for DEA. In these cases, more detailed mechanistic information can be derived by comparing the energy dependent yields of several products [24,26] as will be exemplified in Section 4. In particular cases, a unique assignment can be obtained by exchanging one component of the ice for another and checking whether product formation still occurs [37].
3. How Do Reactive Species Form under Electron Irradiation?
3.1. Basics of Electron Molecule Interactions
3.2. Reactive Intermediates Formed by EI/DI
3.3. Reactive Intermediates from ND
3.4. Reactive Intermediates from (D)EA
3.5. Effect of Condensed Phase
4. How Do Reactive Species Undergo Chemical Transformation in Condensed Phase?
4.1. Radical Recombination
4.2. Transfer Hydrogenation
4.3. Reduction by Hydrogen Radicals
4.4. Hydrogenation by Methoxy Radicals
4.5. Addition Reactions Involving Radical Cations or Neutral Radicals
4.6. Oxidation of CO to CO2
5. Open Questions and Perspectives for Future Studies
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
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NH3 | H2O | CH3OH | |
C2H4 | Ethylamine [29] | Ethanol [28] | Ethyl methyl ether [32] |
CO | Formamide [30] | Formic acid [24] | Methyl formate [26] |
Source Molecule | Reactive Species | Ionization Threshold (Gas Phase) 1 | Threshold for Product Formation (Ice) | References (Ice) |
---|---|---|---|---|
C2H4 | C2H4•+ | 10.5 eV | 8–10 eV | [28,29,32] |
CO | CO•+ | 14.014 eV | 13–14 eV | [30] |
NH3 | NH3•+ | 10.070 eV | ≤12 eV/10 eV | [27,30] |
H2O | H2O•+ | 12.621 eV | 11 eV | [28] |
CH4 | CH4•+ | 12.61 eV | 12 eV | this work |
CH3OH | CH3OH•+ CH3O•+ | 10.84 eV 11.67 eV | 9.8 eV ≤11 eV | [31,32] [32] |
Source Molecule | Reactive Species | Threshold for Product Formation (Ice) | References (Ice) |
---|---|---|---|
NH3 | H• + NH2• | ~7 eV | this work |
H2O | H2 + O H• + HO• | 6–7 eV 6–7 eV | [24] [24,28] |
CH4 | H• + CH3• | ~10 eV | this work |
CH3OH | CH3O• + H• H• + •CH2OH CH3• + HO• | ~6 eV ~6 eV ~6 eV | [31] [31] [31] |
Source Molecule | Reactive Species | Resonance in Product Formation (Ice) | References (Ice) |
---|---|---|---|
C2H4 | C2H4•− | <5 eV | [28] |
CO | CO•− C + O•− | ~4 eV 11 eV/16 eV | [24] [37] |
H2O | H• + HO− O•− + H2 | 6.5 eV 10 eV | [24] [24] |
CH3OH | CH3O• + H− CH3O− + H• | 5.5 eV 5.5 eV | [32] [26,31] |
CH3CN | CH3• + CN− | 4 eV/10 eV | [25] |
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Schmidt, F.; Borrmann, T.; Mues, M.P.; Benter, S.; Swiderek, P.; Bredehöft, J.H. Mechanisms of Electron-Induced Chemistry in Molecular Ices. Atoms 2022, 10, 25. https://doi.org/10.3390/atoms10010025
Schmidt F, Borrmann T, Mues MP, Benter S, Swiderek P, Bredehöft JH. Mechanisms of Electron-Induced Chemistry in Molecular Ices. Atoms. 2022; 10(1):25. https://doi.org/10.3390/atoms10010025
Chicago/Turabian StyleSchmidt, Fabian, Tobias Borrmann, Martin Philipp Mues, Sanna Benter, Petra Swiderek, and Jan Hendrik Bredehöft. 2022. "Mechanisms of Electron-Induced Chemistry in Molecular Ices" Atoms 10, no. 1: 25. https://doi.org/10.3390/atoms10010025