Chemistry:Diatomic carbon

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Diatomic carbon
Dicarbon.svg
Dicarbon-3D-vdW.png
Names
IUPAC name
Diatomic carbon
Systematic IUPAC name
Ethenediylidene (substitutive)
Dicarbon(CC) (additive)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
196
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).
Infobox references

Diatomic carbon (systematically named dicarbon and 2,2λ2-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 form of carbon after atomic carbon, and is an intermediate participator in the genesis of fullerenes.

Properties

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

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
a3Πu 8.5 a3ΠuX1Σ+g 14.0 μm Long-wavelength infrared
b3Σg 77.0 b3Σga3Πu 1.7 μm Short-wavelength infrared
A1Πu 100.4 A1ΠuX1Σ+g
A1Πub3Σg
1.2 μm
5.1 μm
Near infrared
Mid-wavelength infrared
B1Σ+g ? B1Σ+gA1Πu
B1Σ+ga3Πu
?
?
?
?
c3Σ+u 159.3 c3Σ+ub3Σg
c3Σ+uX1Σ+g
c3Σ+uB1Σ+g
1.5 μm
751.0 nm
?
Short-wavelength infrared
Near infrared
?
d3Πg 239.5 d3Πga3Πu
d3Πgc3Σ+u
d3ΠgA1Πu
518.0 nm
1.5 μm
860.0 nm
Green
Short-wavelength infrared
Near infrared
C1Πg 409.9 C1ΠgA1Πu
C1Πga3Πu
C1Πgc3Σ+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

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

C/2014 Q2 (Lovejoy) glows green due to diatomic carbon.

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]

See also

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

References

  1. Hoffmann, Roald (1995). "Marginalia: C2 In All Its Guises". American Scientist 83 (4): 309–311. Bibcode1995AmSci..83..309H. http://www.roaldhoffmann.com/sites/all/files/c2_in_all-_its_guises.pdf. 
  2. 2.0 2.1 2.2 2.3 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. 3.0 3.1 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. 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. doi:10.1038/nchem.1263. PMID 22354433. Bibcode2012NatCh...4..195S. 
  5. Grunenberg, Jörg (2012). "Quantum chemistry: Quadruply bonded carbon". Nature Chemistry 4 (3): 154–155. doi:10.1038/nchem.1274. PMID 22354425. Bibcode2012NatCh...4..154G. 
  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. doi:10.1103/PhysRevB.50.11355. PMID 9975266. Bibcode1994PhRvB..5011355C. 
  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" (in en). Nature Communications 11 (1): 2134. doi:10.1038/s41467-020-16025-x. ISSN 2041-1723. PMID 32358541. Bibcode2020NatCo..11.2134M. 
  9. Rzepa, Henry S. (2021-02-23). "A thermodynamic assessment of the reported room-temperature chemical synthesis of C 2" (in en). Nature Communications 12 (1): 1241. doi:10.1038/s41467-021-21433-8. ISSN 2041-1723. PMID 33623013. Bibcode2021NatCo..12.1241R. 
  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. doi:10.1093/mnras/stw1820. Bibcode2016MNRAS.463.2137V. 
  11. Mikuz, Herman; Dintinjana, Bojan (1994). "CCD Photometry of Comets". International Comet Quarterly. http://www.observatorij.org/CCDPhot/iwca5.html. Retrieved October 26, 2006.