An article in this Journal nicely discusses the visible spectrum of liquid oxygen in the framework of molecular orbital theory applied to the O2 molecule (1). It is very interesting that the simultaneous excitation of two O2 molecules to the first excited state by a single photon accounts for the blue color of oxygen in the liquid and solid phases. Furthermore, the reported results lead to energy values above ground state of 1.576 × 10–19 and 2.62 × 10–19 J per molecule for the first two excited states of the O2 molecule. Multiplied by Avogadro's number, these values give 94.9 and 157.8 kJmol–1, in excellent agreement with the literature values of 94.72 and 157.85 kJmol–1(2). Nevertheless, there is a mistake in the electronic structure of the first two excited states. While the ground state electron configuration of the O2 molecule is
KK (σ2s)2(σ2s*)2(σ2pz)2(π2px)2(π2py)2(π2px*)1(π2py*)1
with the electrons in the π* orbitals with parallel spins (a triplet 3Σg state), in agreement with Hund’s first rule, the first excited state (94.72 kJmol–1 above ground state) has the configuration
KK (σ2s)2(σ2s*)2(σ2pz)2(π2px )2(π2py)2(π2px*)2(π2py*)0
(a singlet 1Δg state) and the second excited state (157.85 kJmol–1 above ground state) is
KK (σ2s)2(σ2s*)2(σ2pz)2(π2px )2(π2py)2(π2px*)1(π2py*)1
with the electrons in the π* orbitals with opposite spins (a singlet 1Σg state) (2–4). The two excited states are interchanged in reference (1), as well as in some inorganic chemistry textbooks (5–7), while other textbooks contain the correct ordering (8–12).
In the excellent textbook by Greenwood and Earnshaw (5), it is correctly stated that the first excited state of the O2 molecule corresponds to the singlet 1Δg state, but it is incorrectly assigned to a configuration with the π* electrons occupying separate orbitals. It is important that the mistake is corrected in further editions of the textbooks (5–7) in order to avoid the disturbing discrepancies that we put forward a few years ago (4). The very interesting discussions in reference (1) are quite valid just by exchanging the configurations of the singlet-1 and singlet-2 states in Figure 1.
Ebsworth, E. A. V.; Connor, J. A.; Turner, J. J. In Comprehensive Inorganic Chemistry; Trotman-Dickenson, A. F., Ed.; Pergamon: Oxford, 1973, Vol 2; p 702.
(a) Bland, J. J. Chem. Educ. 1976, 53, 274; (b) Nardello, V.; Marti, M. J.; Pierlot, C.; Aubry, J. M. J. Chem. Educ. 1999, 76, 1285.
Tudela, D.; Fernández,
V. Educ. Chem. 1994, 31, 150.
Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd ed.; Butterworth-Heinemann: Oxford, UK, 1997; p 605.
Miessler, G. L.; Tarr, D. A. Inorganic Chemistry, 2nd ed.; Prentice-Hall: Upper Saddle River, NJ, 1999; p 260.
Housecroft, C. E.; Sharpe, A. G. Inorganic Chemistry; Pearson Education: Harlow, UK, 2001; p 355.
Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chemistry, 3rd ed.; Wiley: New York, 1995; p 440.
Lee, J. D. Concise Inorganic Chemistry, 5th ed.; Chapman and Hall: London, 1996; p 541.
Shriver, D. F.; Atkins, P. W. Inorganic Chemistry, 3rd ed.; Oxford University Press: Oxford, UK, 1999; p 390.
Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley: New York, 1999; p 452.
Rayner-Canham, G.; Overton, T. Descriptive Inorganic Chemistry, 3rd ed.; Freeman: New York, 2003; p 372.
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Citation
Tudela, David; Fernández, Vicente. J. Chem. Educ.2003 80 1381.
Keywords
General Chemistry; Laboratory Instruction; MO Theory; Oxygen; UV-Vis Spectroscopy
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