Ab initio studies of interoxygen bonding in O2, HO2, H2O2, O3, HO3, and H2O3
1.C. A. Coulson, Valence (Oxford U.P., New York, 1961).
2.L. Pauling, The Nature of the Chemical Bond (Cornell U.P., Ithaca, NY, 1960).
3.(a) S. W. Benson, J. Am. Chem. Soc. 86, 3922 (1964).
3.(b) S. W. Benson, Thermochemical Kinetics (Wiley, New York, 1968).
4.(a) P. A. Giguère and K. Herman, Can. J. Chem. 48, 3473 (1970).
4.(b) X. Deglise and P. A. Giguère, Can. J. Chem. 49, 2242 (1971).
4.(c) P. A. Guiguère, Trans. N.Y. Acad. Sci. 34, 334 (1972)
4.(d) J. L. Arnau and P. A. Giguère, J. Chem. Phys. (to be published);
4.Professor P. A. Giguère (private communication).
4.(e) G. Czapaki and B. H. J. Bielski, J. Phys. Chem. 67, 2180 (1963);
4.B. H. J. Bielski and H. A. Schwarz, J. Phys. Chem. 72, 3836 (1968).
5.R. W. Fessenden, J. Chem. Phys. 48, 3725 (1968).
6.The prototype radical, although so far undetected, has been discussed by Benson.3 Its stability is considered in Sec. IV of the present study.
7.(a) R. P. Hirschmann, W. B. Fox, and L. R. Anderson, Spectrochim. Acta. 25, 811 (1969).
7.(b) J. D. Witt, J. R. Durig, D. Des Marteau, and R. M. Hammaker, Inorg. Chem. 12, 807 (1973).
7.(c) Crystalline di‐tert‐butyl and dicumyl trioxides have been isolated by P. D. Bartlett and M. Lakav, Israel J. Chem. 10, 101 (1972).
8.(a) R. H. Jackson, J. Chem. Soc. 1962, 4585.
8.(b) P. H. Kasai and A. D. Kirshenbaum, J. Am. Chem. Soc. 87, 3069 (1965).
8.(c) R. W. Fessenden and R. H. Schuler, J. Chem. Phys. 44, 434 (1966).
8.(d) R. D. Spratley and G. C. Pimentel, J. Am. Chem. Soc. 88, 2394 (1966).
8.(e) M. D. Newton, W. A. Lathan, W. J. Hehre, and J. A. Pople, J. Chem. Phys. 52, 4064 (1970).
9.(a) W. A. Lathan, W. J. Hehre, and J. A. Pople, J. Am. Chem. Soc. 93, 808 (1971).
9.(b) Calculations for the syn and anti forms of using an assumed framework geometry, have been reported by L. Radom, W. J. Hehre, and J. A. Pople, J. Am. Chem. Soc. 93, 289 (1971).
9.See also B. Plesničar, S. Kaiser, and A. Ažman, J. Amer. Chem. Soc. 95, 5476 (1973).
10.D. Behar, G. Czapski, J. Rabani, L. M. Dorfman, and H. A. Schwarz, J. Phys. Chem. 74, 3209 (1970).
11.For example, H. Levy II, Science 173, 141 (1971).
12.(a) D. E. Milligan and M. E. Jacox, J. Chem. Phys. 38, 2627 (1963).
12.(b) M. E. Jacox and D. E. Milligan, J. Mol. Spectrosc. 42, 495 (1972).
12.(c) For related gas phase work see T. T. Paukert and H. S. Johnston, University of California Radiation Laboratory Report No. UCRL‐19109, November 1969.
13.M. D. Newton, in Abstracts of the 161st Meeting of the American Chemical Society, Los Angeles, California, March 1971.
13.R. J. Blint and M. D. Newton, in Abstracts of the 28th Symposium on Molecular Structure and Spectroscopy, Ohio State University, Columbus, Ohio, June 1973.
14.D. H. Liskow, H. F. Schaefer III, and C. F. Bender, J. Am. Chem. Soc. 93, 6734 (1971).
15.J. L. Gole and E. F. Hayes, J. Chem. Phys. 57, 360 (1972).
16.F. C. Fehsenfeld, M. Moseman, and E. E. Ferguson, J. Chem. Phys. 55, 2115 (1971); the possibility of a role for the species arises from the fact that the driving force for the reaction might require at least a weak bond between the and OH products.
17.The ESR hyperfine data in Ref. 5 suggested an effective planar geometry of the COOO•fragment. The present calculations (Sec. III), indicate that this most likely arises from dynamic interconversion of nonplanar equilibrium structures.
18.1, 2, 3‐Trioxolane can be considered to be a dialkyl derivative of i.e., ethylene trioxide
19.N. L. Bauld, J. A. Thompson, C. E. Hudson, and P. S. Bailey, J. Am. Chem. Soc. 90, 1822 (1968).
20.For a recent theoretical discussion see R. A. Rouse, J. Am. Chem. Soc. 95, 3460 (1973).
21.For a general discussion see H. S. Johnston, Gas Phase Reaction Rate Theory (Ronald, New York, 1966).
22.H. F. Schaefer III, J. Chem. Phys. 54, 2207 (1971).
23.C. C. J. Roothaan, Rev. Mod. Phys. 23, 69 (1951).
24.C. C. J. Roothaan, Rev. Mod. Phys. 32, 179 (1960); the open shell RHF calculations were carried out with a computer program written by W. J. Hunt, P. J. Hay, and W. A. Goddard III.
25.J. A. Pople and R. H. Nesbet, J. Chem. Phys. 22, 571 (1954).
26.R. Ditchfield, W. J. Hehre, and J. S. Pople, J. Chem. Phys. 54, 724 (1971).
27.J. M. Schulman, J. W. Moscowitz, and C. Hollister, J. Chem. Phys. 46, 2759 (1967);
27.D. Neumann and J. W. Moscowitz, J. Chem. Phys. 49, 2056 (1968).
28.While the [32/2] basis is found to be reliable for geometries of the oxygen hydrides, as well as many other molecular systems, it should be noted that some striking exceptions exist; e.g., the bond lengths in 8a found to be poorly accounted for with a minimal basis set,8e are also in serious error (up to 0.2 Å) at the  level. Clearly further study of the oxygen flourides is necessary.8d
29.T. H. Dunning, Jr., J. Chem. Phys. 53, 2823 (1970); the hydrogen atom CGTOs were scaled by the factor
30.T. H. Dunning, Jr., J. Chem. Phys. 55, 3958 (1971).
31.Optimized at the [32/2] level.
32.Assigned the [32/2] optimal value for water.
33.The calculated HOO angles appear to be exaggerated by a few degrees; e.g., the experimental value in (see Ref. 34) is 95°, compared with [32/2] and near‐Hartree‐Fock values of 100.8° and 101.0° [A. Veillard, Chem. Phys. Lett. 4, 51 (1969)], respectively.
34.R. L. Redington, W. B. Olson, and P. C. Cross, J. Chem. Phys. 36, 1311 (1962).
35. and were calculated for the trans‐staggered conformation for reasons of computational economy.
36.See discussion of numerical accuracy in Ref. 8(e).
37.Using computer program SD‐9032 VII, written by J. H. Schachtschneider, as described in Technical Rept. No, 263‐62, Shell Development Co., Emeryville, CA, 1964.
38.The and oxygen bases employed here include nine primitive s‐type GTOs with exponents ranging from 0.28 to while the basis includes eight primitives, with exponents in the range,
39.(a) The force constants were obtained from the sixteen frequencies listed in Ref. 12 for six different isotopic variants (combinations of and ). The frequencies were corrected for anharmonicity as follows: for the bending modes, (see Ref. 34) was added; for the OO stretching modes, corrections of were added, obtained by scaling the anharmonic correction for (Table I, footnote d) proportionally to the magnitude of the observed frequencies; similarly, the corrections for the OH and OD stretching modes were obtained by scaling the average (from and ) anharmonic corrections for and [G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York. 1945)], yielding values of ∼160 and respectively. Regression analysis37 yielded five force constants (the stretch‐stretch interaction constant was omitted): These force constants are generally similar to previous values,12 which were based on observed frequencies without correction for anharmonicity, and an assumed interoxygen distance of 1.300 Å.
39.(b) From the equilibrium geometry and ten harmonic frequencies given in Ref. 34 for and regression analysis37 yielded the following force constants (in terms of symmetrized valence coordinates): A—symmetry: B—symmetry:
40. (see Sec. IV),
41.A more elaborate discussion of this model has been given by Spratley and Pimentel,8d who note that it is especially plausible for the oxygen flourides.
42.P. J. Hay and W. A. Goddard III (private communication).
43.The spin densities, obtained from UHF25 [43/2] wavefunctions, are positive; the negative signs arise from the negative value [F. A. Bovey, Nuclear Magnetic Resonance Spectroscopy (Academic, New York, 1969)].
44.The experimental splitting for the states is 0.98 eV (Footnote d, Table I).
45.T. H. Dunning, Jr. and W. A. Goddard III. Paper V4, presented at the 28th Symposium on Molecular Structure and Spectroscopy. Columbus, Ohio, June 1973 (and private communication).
46.(a) L. Andrews and R. C. Spiker, J. Phys. Chem. 76, 3208 (1972).
46.(b) The microwave structure was determined by R. H. Hughes, J. Chem. Phys. 24, 131 (1956).
47.W. J. Hehre, R. Ditchfield, L. Radom, and J. A. Pople, J. Am. Chem. Soc. 92, 4796 (1970);
47.M. D. Newton and J. M. Schulman, J. Am. Chem. Soc. 94, 767, 773 (1972). The calculated reaction enthalpies, in conjunction with known heats of formation, allow unknown heats of formation (e.g., for and ) to be calculated., J. Am. Chem. Soc.
48.K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds (Wiley‐Interscience, New York, 1969).
49.Y. Morino and S. Saito, J. Mol. Spectrosc. 19, 435 (1966).
50.In is found at 48
51.We note that the calculated frequencies, especially are rather sensitive to the conformation; the quoted values are based on dihedral angles of 90° ( symmetry).
52.H. Wieser, P. J. Kreuger, E. Muller, and J. B. Hyne, Can. J. Chem. 47, 1634 (1969).
53.J. W. Nibler and G. C. Pimentel, J. Mol. Spectrosc. 26, 294 (1968).
54.J. A. Pople, D. L. Beveridge, and P. A. Dobosh, J. Chem. Phys. 47, 2026 (1967).
55.The utility of the CNDO method in analyzing infrared intensities has been studied by G. A. Segal and M. L. Klein, J. Chem. Phys. 47, 4236 (1967).
55.See also D. C. McKean, R. E. Bruns, W. B. Person, and G. A. Segal, J. Chem. Phys. 55, 2890 (1971).
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