Chemistry:Diatomic carbon
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| Names | |
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| IUPAC name
Diatomic carbon
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| Systematic IUPAC name
Ethenediylidene (substitutive) Dicarbon(C—C) (additive) | |
| Identifiers | |
3D model (JSmol)
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| ChEBI | |
| ChemSpider | |
| 196 | |
PubChem CID
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| 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 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 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
transitionRelaxation
wavelengthRelaxation EM-region X1Σ+g 0 – – – a3Πu 8.5 a3Πu→X1Σ+g 14.0 μm Long-wavelength infrared b3Σ−g 77.0 b3Σ−g→a3Πu 1.7 μm Short-wavelength infrared A1Πu 100.4 A1Πu→X1Σ+g
A1Πu→b3Σ−g1.2 μm
5.1 μmNear infrared
Mid-wavelength infraredB1Σ+g ? B1Σ+g→A1Πu
B1Σ+g→a3Πu?
??
?c3Σ+u 159.3 c3Σ+u→b3Σ−g
c3Σ+u→X1Σ+g
c3Σ+u→B1Σ+g1.5 μm
751.0 nm
?Short-wavelength infrared
Near infrared
?d3Πg 239.5 d3Πg→a3Πu
d3Πg→c3Σ+u
d3Πg→A1Πu518.0 nm
1.5 μm
860.0 nmGreen
Short-wavelength infrared
Near infraredC1Πg 409.9 C1Πg→A1Πu
C1Πg→a3Πu
C1Πg→c3Σ+u386.6 nm
298.0 nm
477.4 nmViolet
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
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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
- Acetylide – a related chemical with the formula C2−2
References
- ↑ Hoffmann, Roald (1995). "Marginalia: C2 In All Its Guises". American Scientist 83 (4): 309–311. Bibcode: 1995AmSci..83..309H. http://www.roaldhoffmann.com/sites/all/files/c2_in_all-_its_guises.pdf. Retrieved 2017-07-22.
- ↑ 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.
- ↑ 3.0 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.
- ↑ 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. Bibcode: 2012NatCh...4..195S.
- ↑ Grunenberg, Jörg (2012). "Quantum chemistry: Quadruply bonded carbon". Nature Chemistry 4 (3): 154–155. doi:10.1038/nchem.1274. PMID 22354425. Bibcode: 2012NatCh...4..154G.
- ↑ 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. Bibcode: 1994PhRvB..5011355C.
- ↑ 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.
- ↑ 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. Bibcode: 2020NatCo..11.2134M.
- ↑ 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. Bibcode: 2021NatCo..12.1241R.
- ↑ 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. Bibcode: 2016MNRAS.463.2137V.
- ↑ Mikuz, Herman; Dintinjana, Bojan (1994). "CCD Photometry of Comets". International Comet Quarterly. http://www.observatorij.org/CCDPhot/iwca5.html. Retrieved October 26, 2006.
- ↑ Georgiou, Aristos (2023-01-10). "What makes the green comet green?" (in en). https://www.newsweek.com/green-comet-appear-february-night-sky-never-return-earth-1772429.
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