Jump to content

Diatomic carbon: Difference between revisions

From Wikipedia, the free encyclopedia
Browse history interactively
← Previous edit
Content deleted Content added
VisualWikitext
→History: another green pic of C2
mNo edit summary
Tags: Visual edit Mobile edit Mobile web edit Advanced mobile edit
 
(7 intermediate revisions by 7 users not shown)
Line 31: Line 31:
}}
}}


'''Diatomic carbon''' (systematically named '''dicarbon''' and '''1λ<sup>2</sup>,2λ<sup>2</sup>-ethene'''), is a green, gaseous [[inorganic chemistry|inorganic]] [[chemical]] with the [[chemical formula]] C=C (also written [C<sub>2</sub>] or C<sub>2</sub>). It is kinetically unstable at ambient temperature and pressure, being removed through [[Polymerization|autopolymerisation]]. It occurs in carbon vapor, for example in [[electric arc]]s; in [[comet]]s, [[stellar atmosphere]]s, and the [[interstellar medium]]; and in blue [[hydrocarbon]] [[flame]]s.<ref name="Hoffman1995">{{cite journal| first = Roald| last = Hoffmann| author-link = Roald Hoffmann| title = Marginalia: C<sub>2</sub> In All Its Guises| journal = [[American Scientist]] | year = 1995| url = http://www.roaldhoffmann.com/sites/all/files/c2_in_all-_its_guises.pdf| volume = 83| issue = 4| pages = 309–311| bibcode = 1995AmSci..83..309H| jstor = 29775475}}</ref>
'''Diatomic carbon''' (systematically named '''dicarbon''' and '''1λ<sup>2</sup>,2λ<sup>2</sup>-ethene'''), is a green, gaseous [[inorganic chemistry|inorganic]] [[chemical]] with the [[chemical formula]] C=C (also written [C<sub>2</sub>] or C<sub>2</sub>). It is kinetically unstable at ambient temperature and pressure, being removed through [[Polymerization|autopolymerisation]]. It occurs in carbon vapor, for example in [[electric arc]]s; in [[comet]]s, [[stellar atmosphere]]s, and the [[interstellar medium]]; and in blue [[hydrocarbon]] [[flame]]s.<ref name="Hoffman1995">{{cite journal| first = Roald| last = Hoffmann| author-link = Roald Hoffmann| title = Marginalia: C<sub>2</sub> In All Its Guises| journal = [[American Scientist]]| year = 1995| url = http://www.roaldhoffmann.com/sites/all/files/c2_in_all-_its_guises.pdf| volume = 83| issue = 4| pages = 309–311| bibcode = 1995AmSci..83..309H| jstor = 29775475| access-date = 2017-07-22| archive-date = 2023-03-21| archive-url = https://web.archive.org/web/20230321180249/http://www.roaldhoffmann.com/sites/all/files/c2_in_all-_its_guises.pdf| url-status = dead}}</ref>
Diatomic carbon is the second simplest of the [[allotropes of carbon]] (after [[atomic carbon]]), and is an intermediate participator in the genesis of [[fullerenes]].
Diatomic carbon is the second simplest of the [[allotropes of carbon]] (after [[atomic carbon]]), and is an intermediate participant in the genesis of [[fullerenes]].


== Properties ==
== Properties ==
Line 74: Line 74:
*Singlet C<sub>2</sub> will also react with [[alkene]]s. Acetylene is a main product; however, it appears C<sub>2</sub> will insert into carbon-hydrogen bonds.
*Singlet C<sub>2</sub> will also react with [[alkene]]s. Acetylene is a main product; however, it appears C<sub>2</sub> will insert into carbon-hydrogen bonds.
*C<sub>2</sub> is 2.5 times more likely to insert into a [[methyl group]] as into [[methylene group]]s.<ref name= alkanes>{{cite journal | title = Reaction of Diatomic Carbon with Alkanes and Ethers/ Trapping of Alkylcarbenes by Vinylidene | last1 = Skell | first1 = P. S. | author-link1 = Philip Skell | last2 = Fagone | first2 = F. A. | last3 = Klabunde | first3 = K. J. | journal = [[Journal of the American Chemical Society]] | year = 1972 | volume = 94 | issue = 22 | pages = 7862–7866| doi = 10.1021/ja00777a032}}</ref>
*C<sub>2</sub> is 2.5 times more likely to insert into a [[methyl group]] as into [[methylene group]]s.<ref name= alkanes>{{cite journal | title = Reaction of Diatomic Carbon with Alkanes and Ethers/ Trapping of Alkylcarbenes by Vinylidene | last1 = Skell | first1 = P. S. | author-link1 = Philip Skell | last2 = Fagone | first2 = F. A. | last3 = Klabunde | first3 = K. J. | journal = [[Journal of the American Chemical Society]] | year = 1972 | volume = 94 | issue = 22 | pages = 7862–7866| doi = 10.1021/ja00777a032}}</ref>
* There is a disputed possible room-temperature chemical synthesis via alkynyl-λ<sup>3</sup>-iodane.<ref>{{Cite journal|last1=Miyamoto|first1=Kazunori|last2=Narita|first2=Shodai|last3=Masumoto|first3=Yui|last4=Hashishin|first4=Takahiro|last5=Osawa|first5=Taisei|last6=Kimura|first6=Mutsumi|last7=Ochiai|first7=Masahito|last8=Uchiyama|first8=Masanobu|date=2020-05-01|title=Room-temperature chemical synthesis of C 2|journal=Nature Communications|language=en|volume=11|issue=1|pages=2134|doi=10.1038/s41467-020-16025-x|pmid=32358541|issn=2041-1723|pmc=7195449|bibcode=2020NatCo..11.2134M}}</ref><sup></sup><ref>{{Cite journal|last=Rzepa|first=Henry S.|date=2021-02-23|title=A thermodynamic assessment of the reported room-temperature chemical synthesis of C 2|journal=Nature Communications|language=en|volume=12|issue=1|pages=1241|doi=10.1038/s41467-021-21433-8|pmid=33623013|issn=2041-1723|pmc=7902603|bibcode=2021NatCo..12.1241R}}</ref>
* There is a disputed possible room-temperature chemical synthesis via alkynyl-λ<sup>3</sup>-iodane.<ref>{{Cite journal|last1=Miyamoto|first1=Kazunori|last2=Narita|first2=Shodai|last3=Masumoto|first3=Yui|last4=Hashishin|first4=Takahiro|last5=Osawa|first5=Taisei|last6=Kimura|first6=Mutsumi|last7=Ochiai|first7=Masahito|last8=Uchiyama|first8=Masanobu|date=2020-05-01|title=Room-temperature chemical synthesis of C 2|journal=Nature Communications|language=en|volume=11|issue=1|pages=2134|doi=10.1038/s41467-020-16025-x|pmid=32358541|issn=2041-1723|pmc=7195449|bibcode=2020NatCo..11.2134M}}</ref><ref>{{Cite journal|last=Rzepa|first=Henry S.|date=2021-02-23|title=A thermodynamic assessment of the reported room-temperature chemical synthesis of C 2|journal=Nature Communications|language=en|volume=12|issue=1|pages=1241|doi=10.1038/s41467-021-21433-8|pmid=33623013|issn=2041-1723|pmc=7902603|bibcode=2021NatCo..12.1241R}}</ref>


== History ==
== History ==
[[File:C2014Q2 Lovejoy by Paul Stewart.png|thumb|[[C/2014 Q2]] (Lovejoy) glows green due to diatomic carbon.]]
[[File:C2014Q2 Lovejoy by Paul Stewart.png|thumb|[[C/2014 Q2]] (Lovejoy) glows green due to diatomic carbon.]]
[[File:C2022 E3 (ZTF)- Alessandro Bianconi.png|thumb|[[C/2022 E3 (ZTF)]] also looks green.]]
[[File:C2022 E3 (ZTF)- Alessandro Bianconi.jpg|thumb|[[C/2022 E3 (ZTF)]] also looks green.]]
The light of gas rich comets mainly originates from the emission of diatomic carbon. An example is [[C/2014 Q2 (Lovejoy)]], where there are several lines of C<sub>2</sub> light, mostly in the [[visible spectrum]]<ref name = "C2014Q2Spec"> {{cite journal |first1 = Kumar | last1 = Venkataramani
The light of gas-rich comets mainly originates from the emission of diatomic carbon. An example is [[C/2014 Q2 (Lovejoy)]], where there are several lines of C<sub>2</sub> light, mostly in the [[visible spectrum]],<ref name = "C2014Q2Spec">{{cite journal |first1 = Kumar | last1 = Venkataramani
|first2 = Satyesh | last2 = Ghetiya
|first2 = Satyesh | last2 = Ghetiya
|first3 = Shashikiran | last3 = Ganesh
|first3 = Shashikiran | last3 = Ganesh
Line 85: Line 85:
|title = Optical spectroscopy of comet C/2014 Q2 (Lovejoy) from the Mount Abu Infrared Observatory
|title = Optical spectroscopy of comet C/2014 Q2 (Lovejoy) from the Mount Abu Infrared Observatory
| journal = [[Monthly Notices of the Royal Astronomical Society]]
| journal = [[Monthly Notices of the Royal Astronomical Society]]
| year = 2016 |volume = 463 |issue = 2 |pages = 2137–2144 |doi = 10.1093/mnras/stw1820 |arxiv = 1607.06682 | bibcode = 2016MNRAS.463.2137V
| year = 2016 |volume = 463 |issue = 2 |pages = 2137–2144 |doi = 10.1093/mnras/stw1820 | doi-access = free
|arxiv = 1607.06682 | bibcode = 2016MNRAS.463.2137V
⚫
}}</ref> forming the [[Swan band]]s.<ref name="CrniVrhObservatory">{{cite journal | url = http://www.observatorij.org/CCDPhot/iwca5.html
}}</ref>
⚫
, forming the [[Swan band]]s.<ref name="CrniVrhObservatory">{{cite journal | url = http://www.observatorij.org/CCDPhot/iwca5.html
| first1 = Herman | last1 = Mikuz
| first1 = Herman | last1 = Mikuz
| first2 = Bojan | last2 = Dintinjana
| first2 = Bojan | last2 = Dintinjana
Line 100: Line 100:
== References ==
== References ==
{{reflist}}
{{reflist}}

{{allotropes of carbon}}
{{Allotropes of carbon}}
{{diatomicelements}}
{{Diatomic elements}}
{{Molecules detected in outer space}}
{{Molecules detected in outer space}}


Latest revision as of 05:48, 19 November 2024

Diatomic carbon
Names
IUPAC name
Diatomic carbon
Systematic IUPAC name
Ethenediylidene (substitutive)
Dicarbon(C—C) (additive)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
196
  • InChI=1S/C2/c1-2 checkY
    Key: LBVWYGNGGJURHQ-UHFFFAOYSA-N checkY
  • [C]=[C]
Properties
C2
Molar mass 24.022 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Diatomic carbon (systematically named dicarbon and 1λ2,2λ2-ethene), is a green, gaseous inorganic chemical with the chemical formula C=C (also written [C2] or C2). It is kinetically unstable at ambient temperature and pressure, being removed through autopolymerisation. It occurs in carbon vapor, for example in electric arcs; in comets, stellar atmospheres, and the interstellar medium; and in blue hydrocarbon flames.[1] Diatomic carbon is the second simplest of the allotropes of carbon (after atomic carbon), and is an intermediate participant in the genesis of fullerenes.

Properties

[edit]

C2 is a component of carbon vapor. One paper estimates that carbon vapor is around 28% diatomic,[2] but theoretically this depends on the temperature and pressure.

Electromagnetic properties

[edit]

The electrons in diatomic carbon are distributed among the molecular orbitals according to the Aufbau principle to produce unique quantum states, with corresponding energy levels. The state with the lowest energy level, or ground state, is a singlet state (1Σ+
g), which is systematically named ethene-1,2-diylidene or dicarbon(0•). There are several excited singlet and triplet states that are relatively close in energy to the ground state, which form significant proportions of a sample of dicarbon under ambient conditions. When most of these excited states undergo photochemical relaxation, they emit in the infrared region of the electromagnetic spectrum. However, one state in particular emits in the green region. That state is a triplet state (3Πg), which is systematically named ethene-μ,μ-diyl-μ-ylidene or dicarbon(2•). In addition, there is an excited state somewhat further in energy from the ground state, which only form a significant proportion of a sample of dicarbon under mid-ultraviolet irradiation. Upon relaxation, this excited state fluoresces in the violet region and phosphoresces in the blue region. This state is also a singlet state (1Πg), which is also named ethene-μ,μ-diyl-μ-ylidene or dicarbon(2•).

State Excitation
enthalpy
(kJ mol−1)		 Relaxation
transition		 Relaxation
wavelength		 Relaxation EM-region
X1Σ+
g		 0 – – –
a3Π
u		 8.5 a3Π
u→X1Σ+
g		 14.0 μm Long-wavelength infrared
b3Σ−
g		 77.0 b3Σ−
g→a3Π
u		 1.7 μm Short-wavelength infrared
A1Π
u		 100.4 A1Π
u→X1Σ+
g
A1Π
u→b3Σ−
g		 1.2 μm
5.1 μm		 Near infrared
Mid-wavelength infrared
B1Σ+
g		 ? B1Σ+
g→A1Π
u
B1Σ+
g→a3Π
u		 ?
?		 ?
?
c3Σ+
u		 159.3 c3Σ+
u→b3Σ−
g
c3Σ+
u→X1Σ+
g
c3Σ+
u→B1Σ+
g		 1.5 μm
751.0 nm
?		 Short-wavelength infrared
Near infrared
?
d3Π
g		 239.5 d3Π
g→a3Π
u
d3Π
g→c3Σ+
u
d3Π
g→A1Π
u		 518.0 nm
1.5 μm
860.0 nm		 Green
Short-wavelength infrared
Near infrared
C1Π
g		 409.9 C1Π
g→A1Π
u
C1Π
g→a3Π
u
C1Π
g→c3Σ+
u		 386.6 nm
298.0 nm
477.4 nm		 Violet
Mid-ultraviolet
Blue

Molecular orbital theory shows that there are two sets of paired electrons in a degenerate pi bonding set of orbitals. This gives a bond order of 2, meaning that there should exist a double bond between the two carbon atoms in a C2 molecule.[3] One analysis suggested instead that a quadruple bond exists,[4] an interpretation that was disputed.[5] CASSCF calculations indicate that the quadruple bond based on molecular orbital theory is also reasonable.[3] Bond dissociation energies (BDE) of B2, C2, and N2 show increasing BDE, indicating single, double, and triple bonds, respectively.

In certain forms of crystalline carbon, such as diamond and graphite, a saddle point or "hump" occurs at the bond site in the charge density. The triplet state of C2 does follow this trend. However, the singlet state of C2 acts more like silicon or germanium; that is, the charge density has a maximum at the bond site.[6]

Reactions

[edit]

Diatomic carbon will react with acetone and acetaldehyde to produce acetylene by two different pathways.[2]

  • Triplet C2 molecules will react through an intermolecular pathway, which is shown to exhibit diradical character. The intermediate for this pathway is the ethylene radical. Its abstraction is correlated with bond energies.[2]
  • Singlet C2 molecules will react through an intramolecular, nonradical pathway in which two hydrogen atoms will be taken away from one molecule. The intermediate for this pathway is singlet vinylidene. The singlet reaction can happen through a 1,1-diabstraction or a 1,2-diabstraction. This reaction is insensitive to isotope substitution. The different abstractions are possibly due to the spatial orientations of the collisions rather than the bond energies.[2]
  • Singlet C2 will also react with alkenes. Acetylene is a main product; however, it appears C2 will insert into carbon-hydrogen bonds.
  • C2 is 2.5 times more likely to insert into a methyl group as into methylene groups.[7]
  • There is a disputed possible room-temperature chemical synthesis via alkynyl-λ3-iodane.[8][9]

History

[edit]
C/2014 Q2 (Lovejoy) glows green due to diatomic carbon.
C/2022 E3 (ZTF) also looks green.

The light of gas-rich comets mainly originates from the emission of diatomic carbon. An example is C/2014 Q2 (Lovejoy), where there are several lines of C2 light, mostly in the visible spectrum,[10] forming the Swan bands.[11] C/2022 E3 (ZTF), visible in early 2023, also exhibits green color due to the presence of diatomic carbon.[12]

See also

[edit]
  • Acetylide – a related chemical with the formula C2−
    2

References

[edit]
  1. ^ Hoffmann, Roald (1995). "Marginalia: C2 In All Its Guises" (PDF). American Scientist. 83 (4): 309–311. Bibcode:1995AmSci..83..309H. JSTOR 29775475. Archived from the original (PDF) on 2023-03-21. Retrieved 2017-07-22.
  2. ^ a b c d Skell, Philip S.; Plonka, James H. (1970). "Chemistry of the singlet and triplet C2 molecules. Mechanism of acetylene formation from reaction with acetone and acetaldehyde". Journal of the American Chemical Society. 92 (19): 5620–5624. doi:10.1021/ja00722a014.
  3. ^ a b Zhong, Ronglin; Zhang, Min; Xu, Hongliang; Su, Zhongmin (2016). "Latent harmony in dicarbon between VB and MO theories through orthogonal hybridization of 3σg and 2σu". Chemical Science. 7 (2): 1028–1032. doi:10.1039/c5sc03437j. PMC 5954846. PMID 29896370.
  4. ^ Shaik, Sason; Danovich, David; Wu, Wei; Su, Peifeng; Rzepa, Henry S.; Hiberty, Philippe C. (2012). "Quadruple bonding in C2 and analogous eight-valence electron species". Nature Chemistry. 4 (3): 195–200. Bibcode:2012NatCh...4..195S. doi:10.1038/nchem.1263. PMID 22354433.
  5. ^ Grunenberg, Jörg (2012). "Quantum chemistry: Quadruply bonded carbon". Nature Chemistry. 4 (3): 154–155. Bibcode:2012NatCh...4..154G. doi:10.1038/nchem.1274. PMID 22354425.
  6. ^ Chelikowsky, James R.; Troullier, N.; Wu, K.; Saad, Y. (1994). "Higher-order finite-difference pseudopotential method: An application to diatomic molecules". Physical Review B. 50 (16): 11356–11364. Bibcode:1994PhRvB..5011355C. doi:10.1103/PhysRevB.50.11355. PMID 9975266.
  7. ^ Skell, P. S.; Fagone, F. A.; Klabunde, K. J. (1972). "Reaction of Diatomic Carbon with Alkanes and Ethers/ Trapping of Alkylcarbenes by Vinylidene". Journal of the American Chemical Society. 94 (22): 7862–7866. doi:10.1021/ja00777a032.
  8. ^ Miyamoto, Kazunori; Narita, Shodai; Masumoto, Yui; Hashishin, Takahiro; Osawa, Taisei; Kimura, Mutsumi; Ochiai, Masahito; Uchiyama, Masanobu (2020-05-01). "Room-temperature chemical synthesis of C 2". Nature Communications. 11 (1): 2134. Bibcode:2020NatCo..11.2134M. doi:10.1038/s41467-020-16025-x. ISSN 2041-1723. PMC 7195449. PMID 32358541.
  9. ^ Rzepa, Henry S. (2021-02-23). "A thermodynamic assessment of the reported room-temperature chemical synthesis of C 2". Nature Communications. 12 (1): 1241. Bibcode:2021NatCo..12.1241R. doi:10.1038/s41467-021-21433-8. ISSN 2041-1723. PMC 7902603. PMID 33623013.
  10. ^ Venkataramani, Kumar; Ghetiya, Satyesh; Ganesh, Shashikiran; et, al. (2016). "Optical spectroscopy of comet C/2014 Q2 (Lovejoy) from the Mount Abu Infrared Observatory". Monthly Notices of the Royal Astronomical Society. 463 (2): 2137–2144. arXiv:1607.06682. Bibcode:2016MNRAS.463.2137V. doi:10.1093/mnras/stw1820.
  11. ^ Mikuz, Herman; Dintinjana, Bojan (1994). "CCD Photometry of Comets". International Comet Quarterly. Retrieved October 26, 2006.
  12. ^ Georgiou, Aristos (2023-01-10). "What makes the green comet green?". Newsweek. Archived from the original on 2023-01-25. Retrieved 2023-01-25.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Diatomic_carbon&oldid=1258350927"