Laboratory Studies of Ion/Molecule Reactions of Fullerenes: Chemical Derivatization of Fullerenes within Dense Interstellar Clouds and Circumstellar Shells

Petrie, Simon; Böhme, Diethard K.

doi:10.1086/309346

Cited by 44 publications

(54 citation statements)

References 105 publications

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“…Millar 1992;Petrie & Bohme 2000) and about whether they might play a significant role in interstellar chemistry like PAHs (see e.g. Lepp et al 1988).…”

Section: Chemistry -Preliminary Remarksmentioning

confidence: 99%

Interstellar fullerene compounds and diffuse interstellar bands

Omont

2016

A&A

103

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Recently, the presence of fullerenes in the interstellar medium (ISM) has been confirmed and new findings suggest that these fullerenes may possibly form from polycyclic aromatic hydrocarbons (PAHs) in the ISM. Moreover, the first confirmed identification of two strong diffuse interstellar bands (DIBs) with the fullerene, C + 60 , connects the long standing suggestion that various fullerenes could be DIB carriers. These new discoveries justify reassessing the overall importance of interstellar fullerene compounds, including fullerenes of various sizes with endohedral or exohedral inclusions and heterofullerenes (EEHFs). The phenomenology of fullerene compounds is complex. In addition to fullerene formation in grain shattering, fullerene formation from fully dehydrogenated PAHs in diffuse interstellar clouds could perhaps transform a significant percentage of the tail of low-mass PAH distribution into fullerenes including EEHFs. But many uncertain processes make it extremely difficult to assess their expected abundance, composition and size distribution, except for the substantial abundance measured for C + 60 . EEHFs share many properties with pure fullerenes, such as C 60 , as regards stability, formation/destruction and chemical processes, as well as many basic spectral features. Because DIBs are ubiquitous in all lines of sight in the ISM, we address several questions about the interstellar importance of various EEHFs, especially as possible carriers of diffuse interstellar bands. Specifically, we discuss basic interstellar properties and the likely contributions of fullerenes of various sizes and their charged counterparts such as C + 60 , and then in turn: 1) metallofullerenes; 2) heterofullerenes; 3) fulleranes; 4) fullerene-PAH compounds; 5) H 2 @C 60 . From this reassessment of the literature and from combining it with known DIB line identifications, we conclude that the general landscape of interstellar fullerene compounds is probably much richer than heretofore realized. EEHFs, together with pure fullerenes of various sizes, have many properties necessary to be suitably carriers of DIBs: carbonaceous nature; stability and resilience in the harsh conditions of the ISM; existing with various heteroatoms and ionization states; relatively easy formation; few stable isomers; spectral lines in the right spectral range; various and complex energy internal conversion; rich Jahn-Teller fine structure. This is supported by the first identification of a DIB carrier as C + 60 . Unfortunately, the lack of any precise information about the complex optical spectra of EEHFs and most pure fullerenes other than C 60 and about their interstellar abundances still precludes definitive assessment of the importance of fullerene compounds as DIB carriers. Their compounds could significantly contribute to DIBs, but it still seems difficult that they are the only important DIB carriers. Regardless, DIBs appear as the most promising way of tracing the interstellar abundances of various fullerene compounds if the breakthr...

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“…Millar 1992;Petrie & Bohme 2000) and about whether they might play a significant role in interstellar chemistry like PAHs (see e.g. Lepp et al 1988).…”

Section: Chemistry -Preliminary Remarksmentioning

confidence: 99%

Interstellar fullerene compounds and diffuse interstellar bands

Omont

2016

A&A

103

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“…16 Kroto et al 17 had already conjectured that fullerenes or their derivatives may be major constituents of circumstellar shells with high carbon content or interstellar dust, catalyze reactions of new molecules in space, and be the carrier of the diffuse interstellar bands (DIBs), but early mass spectrometric evidence for extraterrestrial fullerenes in the carbonaceous impact residue in a crater on a spacecraft 18 or spectroscopic identification of fullerene cations in interstellar absorption bands 19 remained ambivalent. 20,21 Hydrogen inhibits the formation of fullerenes in an arc discharge 22 but very high (≥3500 K) temperatures may lead to fullerenes even if hydrogen is present. 23 Interstellar fullerenes may also originate from the envelopes surrounding mass-losing, hydrogen-deficient carbon-rich stars such as R Coronae Borealis (RCB).…”

Section: Introductionmentioning

confidence: 99%

“…23 Interstellar fullerenes may also originate from the envelopes surrounding mass-losing, hydrogen-deficient carbon-rich stars such as R Coronae Borealis (RCB). 20 Recently, conclusive spectroscopic evidence for the existence of cold neutral fullerenes has been identified in IR spectra recorded by the Spitzer Space telescope in planetary nebulae. 24 Remarkably, they are estimated to represent a few percent of the total available cosmic carbon in those regions.…”

Section: Introductionmentioning

confidence: 99%

Adsorption of hydrogen on neutral and charged fullerene: Experiment and theory

Kaiser

Leidlmair

Bartl

et al. 2013

The Journal of Chemical Physics

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A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu The Journal of Chemical Physics 132, 154104 (2010) Helium droplets are doped with fullerenes (either C 60 or C 70 ) and hydrogen (H 2 or D 2 ) and investigated by high-resolution mass spectrometry. In addition to pure helium and hydrogen cluster ions, hydrogen-fullerene complexes are observed upon electron ionization. The composition of the main ion series is (H 2 ) n HC m + where m = 60 or 70. Another series of even-numbered ions, (H 2 ) n C m + , is slightly weaker in stark contrast to pure hydrogen cluster ions for which the even-numbered series (H 2 ) n + is barely detectable. The ion series (H 2 ) n HC m + and (H 2 ) n C m + exhibit abrupt drops in ion abundance at n = 32 for C 60 and 37 for C 70 , indicating formation of an energetically favorable commensurate phase, with each face of the fullerene ion being covered by one adsorbate molecule. However, the first solvation layer is not complete until a total of 49 H 2 are adsorbed on C 60 + ; the corresponding value for C 70 + is 51. Surprisingly, these values do not exhibit a hydrogen-deuterium isotope effect even though the isotope effect for H 2 /D 2 adsorbates on graphite exceeds 6%. We also observe doubly charged fullerene-deuterium clusters; they, too, exhibit abrupt drops in ion abundance at n = 32 and 37 for C 60 and C 70 , respectively. The findings imply that the charge is localized on the fullerene, stabilizing the system against charge separation. Density functional calculations for C 60 -hydrogen complexes with up to five hydrogen atoms provide insight into the experimental findings and the structure of the ions. The binding energy of physisorbed H 2 is 57 meV for H 2 C 60 + and (H 2 ) 2 C 60 + , and slightly above 70 meV for H 2 HC 60 + and (H 2 ) 2 HC 60 + . The lone hydrogen in the odd-numbered complexes is covalently bound atop a carbon atom but a large barrier of 1.69 eV impedes chemisorption of the H 2 molecules. Calculations for neutral and doubly charged complexes are presented as well.

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“…Fullerene cations may undergo multiple addition of atomic hydrogen, forming hydrogenated derivatives (Petrie et al 1995). Neutral fullerenes also add atomic hydrogen easily at very low temperatures (Howard 1993), so that it is reasonable to think that fulleranes, the hydrogenated fullerene derivatives, should be present in the interstellar medium (Petrie and Bohme 2000;Cataldo and Iglesias-Groth 2010).…”

Section: Key Research Findingsmentioning

confidence: 99%

Facula, Faculae

Wagner¹

2015

Encyclopedia of Astrobiology

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Laboratory Studies of Ion/Molecule Reactions of Fullerenes: Chemical Derivatization of Fullerenes within Dense Interstellar Clouds and Circumstellar Shells

Cited by 44 publications

References 105 publications

Interstellar fullerene compounds and diffuse interstellar bands

Interstellar fullerene compounds and diffuse interstellar bands

Adsorption of hydrogen on neutral and charged fullerene: Experiment and theory

Facula, Faculae

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