On the <span class="aps-inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><mrow><mmultiscripts><mrow><mi>Π</mi></mrow><mrow><mi>u</mi></mrow><mrow></mrow><mrow></mrow><mrow></mrow><mprescripts></mprescripts><mrow></mrow><mrow><mn>2</mn></mrow><mrow></mrow><mrow></mrow></mmultiscripts></mrow><mo>→</mo><mrow><mmultiscripts><mrow><mi>Π</mi></mrow><mrow><mi>g</mi></mrow><mrow></mrow><mrow></mrow><mrow></mrow><mprescripts></mprescripts><mrow></mrow><mrow><mn>2</mn></mrow><mrow></mrow><mrow></mrow></mmultiscripts></mrow></math></span> Bands of C<span class="aps-inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><mrow><mmultiscripts><mrow><mi mathvariant="normal">O</mi></mrow><mrow><mn>2</mn></mrow><mrow></mrow><mrow></mrow><mrow><mo>+</mo></mrow></mmultiscripts></mrow></math></span>. Part I

S. Mrozowski

doi:10.1103/PhysRev.60.730

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On the ${}^{2}Π_{u} \to {}^{2}Π_{g}$ Bands of C $O_{2}^{+}$ . Part I

S. Mrozowski

Ryerson Physical Laboratory, University of Chicago, Chicago, Illinois

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Phys. Rev. 60, 730 – Published 15 November, 1941

DOI: https://doi.org/10.1103/PhysRev.60.730

Abstract

The band spectrum appearing in emission in the region $λ 2900 - 4300$ and believed to belong to the C $O_{2}^{+}$ or possibly C $O_{2}$ molecule has been studied and the excitation conditions found to be in substantial agreement with the former results of Duffendack and collaborators and of Smyth. The bands have been obtained with great intensity and photographs of most of them have been made in the second order of the 30-foot grating (actually obtained resolving power of 350,000). The rotational structure and the excitation conditions show that most of the bands belong to an extensive ${}^{2}Π \to {}^{2}Π$ system of bands of the molecule C $O_{2}^{+}$ . The molecule is linear in both states; the lower ${}^{2}Π$ appears to be the ground state ${}^{2}Π_{g}$ and the upper ${}^{2}Π$ is the first excited state ${}^{2}Π_{u}$ of this molecule predicted by Mulliken. The complete rotational and vibrational analysis of this band system is still in progress; in this paper the analysis of 5 double bands of the ${v^{''}}_{1} = {v^{''}}_{2} = {v^{''}}_{3} = 0$ progression of the symmetrical vibration ( ${v^{'}}_{1}$ varying, ${v^{'}}_{2} = {v^{'}}_{3} = 0$ ) is presented. The results of the analysis are: ${ν_{0}}^{(0, 0)} = 28, 532.60 ({}^{2}Π_{\frac{3}{2}} \to {}^{2}Π_{\frac{3}{2}})$ and ${ν_{0}}^{(0, 0)} = 28, 468.48 ({}^{2}Π_{\frac{1}{2}} \to {}^{2}Π_{\frac{1}{2}})$ . The vibrational intervals (i.e., the distances between the origins of successive bands in the progression) are: $Δ {G^{'}}_{1} = 1126.71$ ; $Δ {G^{'}}_{2} = 1122.66$ ; $Δ {G^{'}}_{3} = 1120.22$ ; $Δ {G^{'}}_{4} = 1120.04$ (all ${}^{2}Π_{\frac{3}{2 u}}$ ) and $Δ {G^{'}}_{1} = 1125.97$ ; $Δ {G^{'}}_{2} = 1120.79$ ; $Δ {G^{'}}_{3} = 1116.09$ ; $Δ {G^{'}}_{4} = 1111.76$ (all ${}^{2}Π_{\frac{1}{2} u}$ ). Further for ${}^{2}Π_{\frac{3}{2} g} {B^{''}}_{0} = 0.3796$ ; for ${}^{2}Π_{\frac{1}{2} g} {B^{''}}_{0} = 0.3812$ ; for ${}^{2}Π_{\frac{3}{2} u} {B^{'}}_{0} = 0.3485$ ; ${B^{'}}_{1} = 0.3475$ ; ${B^{'}}_{2} = 0.3465$ ; ${B^{'}}_{3} = 0.3457$ ; ${B^{'}}_{4} = 0.3453$ ; for ${}^{2}Π_{\frac{1}{2} u} {B^{'}}_{0} = 0.3501$ ; ${B^{'}}_{1} = 0.3492$ ; ${B^{'}}_{2} = 0.3483$ ; ${B^{'}}_{3} = 0.3475$ ; ${B^{'}}_{4} = 0.3466$ . The $Λ$ -doubling is observable only is the ${}^{2}Π_{\frac{1}{2}} \to {}^{2}Π_{\frac{1}{2}}$ sub-bands in this progression; in ${}^{2}Π_{u}$ it is bigger than in ${}^{2}Π_{g}$ ( ${p^{''}}_{0} = 0.004$ for ${v^{''}}_{1} = 0$ ) and increases fast with the vibrational energy.

References (19)

G. W. Fox, O. S. Duffendack and E. F. Baker, Proc. Nat. Acad. 13, 320 (1927)
O. S. Duffendack and G. W. Fox, Astrophys. J. 65, 234 (1927)
O. S. Duffendack and H. L. Smith, Phys. Rev. 34, 68 (1929)
H. D. Smyth, Phys. Rev. 38, 2000 (1931) ibid.39, 380 (1932)
J. F. Duncan, Phys. Rev. 34, 1148 (1929)
R. F. Schmid, Phys. Rev. 41, 732 (1932)
R. S. Mulliken, Phys. Rev. 42, 364 (1932)
R. Schmid, Zeits. f. Physik 83, 711 (1933)
R. Schmid, Zeits. f. Physik 84, 732 (1933)
R. Schmid, Zeits. f. Physik 85, 384 (1933)
A. S. Roy and O. S. Duffendack, Proc. Nat. Acad. 19, 497 (1933)
R. S. Mulliken, J. Chem. Phys. 3, 720 (1935)
W. C. Price and (Miss) D. M. Simpson, Proc. Roy. Soc. 169, 501 (1939)
F. Bueso-Sanllehi, Phys. Rev. 60, 556 (1941)
S. Mrozowski, Phys. Rev. 58, 1086 (1940)
W. E. Williams and A. Middleton, Proc. Roy. Soc. 172, 159 (1939)
R. S. Mulliken, Rev. Mod. Phys. 2, 113 (1930)
R. S. Mulliken and A. Christy, Phys. Rev. 38, 87 (1931)
p. 262 in Herzberg's book on Molecular Spectra and Molecular Structure, Vol. I (New York, 1939)

[c1] G. W. Fox, O. S. Duffendack and E. F. Baker, Proc. Nat. Acad. 13, 320 (1927)

[c2] O. S. Duffendack and G. W. Fox, Astrophys. J. 65, 234 (1927)

[c3] O. S. Duffendack and H. L. Smith, Phys. Rev. 34, 68 (1929)

[c4] H. D. Smyth, Phys. Rev. 38, 2000 (1931) ibid.39, 380 (1932)

[c5] J. F. Duncan, Phys. Rev. 34, 1148 (1929)

[c6] R. F. Schmid, Phys. Rev. 41, 732 (1932)

[c7] R. S. Mulliken, Phys. Rev. 42, 364 (1932)

[c8] R. Schmid, Zeits. f. Physik 83, 711 (1933)

[c9] R. Schmid, Zeits. f. Physik 84, 732 (1933)

[c10] R. Schmid, Zeits. f. Physik 85, 384 (1933)

[c11] A. S. Roy and O. S. Duffendack, Proc. Nat. Acad. 19, 497 (1933)

[c12] R. S. Mulliken, J. Chem. Phys. 3, 720 (1935)

[c13] W. C. Price and (Miss) D. M. Simpson, Proc. Roy. Soc. 169, 501 (1939)

[c14] F. Bueso-Sanllehi, Phys. Rev. 60, 556 (1941)

[c15] S. Mrozowski, Phys. Rev. 58, 1086 (1940)

[c16] W. E. Williams and A. Middleton, Proc. Roy. Soc. 172, 159 (1939)

[c17] R. S. Mulliken, Rev. Mod. Phys. 2, 113 (1930)

[c18] R. S. Mulliken and A. Christy, Phys. Rev. 38, 87 (1931)

[c19] p. 262 in Herzberg's book on Molecular Spectra and Molecular Structure, Vol. I (New York, 1939)

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On the ${}^{2}Π_{u} \to {}^{2}Π_{g}$ Bands of C $O_{2}^{+}$ . Part I

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On the Πu2→Πg2 Bands of CO2+. Part I

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On the ${}^{2}Π_{u} \to {}^{2}Π_{g}$ Bands of C $O_{2}^{+}$ . Part I