reciprocal of temperature and the alteration in line widths strongly support the described mechanism. where tAand tB are the lifetimes of the A and B forms. We are presently unwilling to commit ourselves on the In the limit of rapid exchange, the observed sodium mechanism leading to the slow increase in the sodium splitting, a, is given by coupling constant in 2,6-di-t-butylnaphthalene at higher temperatures ; however, we feel that slight changes in the structure of the tight ion pair could account for this variation. The presence of a second weakly associated ion pair may also account for Reddoch’se The contribution of the exchange to the line width of the observations of slight changes in the proton coupling sodium line can be determined by the standard pro- constants, upon dilution, in the anthracene radical cedure.s anion. Detailed studies on the structure and equilibria in- volving ion pairs and their connection to the kinetics of rapid electron-transfer reactions are now in progress In this equation WA and WB represent the resonant and will be reported later. frequencies of the two types of ion pairs considered. (9) A. H.Reddoch, J. Chem. Phys., 43,225 (1965). Values of K were determined for various temperatures through use of eq 1. We estimated the values of aA Noboru Hirota and aB to be 1.55 gauss and 0, respectively, for both Department of Chemistry State University of New York at Stony Brook systems under consideration. These values were ob- Stony Brook, New York tained by extrapolating to the high- and low-temperature limits of the sharp fall-off region. The equilibrium be- Robert Kreilick tween A and B is thought to be between tightly associ- Department of Chemistry, University of Rochester Rochester, New York ated ion pairs, A, and loosely associated ion pairs, B. Received November 13, I965 A plot of log K YS. 1/T yields satisfactory straight lines for both systems. The slope of the lines gives AH = -4.5 kcal for the anthracene case and -4.6 The Fluorides and Oxides of Helium and Neon’ kcal for the di-t-butylnaphthalene case. The entropy change was estimated to be -22 eu for the anthracene Sir : case and -21 eu for the di-t-butylnaphthalene case. High-accuracy, many-electron, valence-bond wave The end of the epr spectrum of anthracene, at various functions have been obtained for HeO, HeF, NeO, temperatures, is “shown in Figure 2 along with stick NeF, and NeF2. As shown in Figure 1, the potential diagrams which show the position and relative intensi- energy curves for all of these species are repulsive ties of the lines. Analogous results were obtained for (for NeF2 and HeF2 the linear molecule in a symmetric di-t-butylnaphthalene. It is seen that at lower tem- stretch is plotted). The method of forming the wave peratures the line width depends on the magnetic functions is the same as that previously reported for quantum number of the sodium nucleus, MZNA. HeF2, and the NeF2 result represents the highest Peaks with MZNA= =k3l2broaden more rapidly than precision quantum-mechanical solution yet achieved peaks with MZNA= * l/2. Since WA - WB is 3/2- for a molecular system with this number of electrons. aAy for peaks with MzNA= =i= and ‘12aAyfor peaks The existence of H e 0 has been predicted by Jsrgen- with MZKA= =k ll2, this variation in line width is sen,3 and Noyes4 has predicted N e 0 and NeF. Their expected when the rate of conversion between A and B work employs reasonable and accepted chemical argu- approaches the hyperfine frequency. ments. Considerable effort has been expended on at- Through the use of eq 2, we have analyzed our data tempts at the synthesis of HeF2 and NeF2 by a number to give estimates of the lifetimes of species A and B. of laboratories. It is also interesting to note that while At - 5 5 O , t A and t B are 1 x 10-8 and 3 x sec, the repulsive potential surfaces of Figure 1 can be respectively, for the anthracene case and 4 X roughly related to the high ionization potentials of and 2 X sec for the di-t-butylnaphthalene case. helium and neon, the ordering of the curves does not The values of AH and AS obtained are similar in follow the ordering of the ionization potentials (or magnitude to those estimated for the dissociation of the electronegativities) of the participating atoms. All of sodium naphthalide ion pair. A similar discussion to these research efforts illustrate the general paucity and that given in ref 2 can be used to explain these values. desirability of truly quantitative electronic structure A large negative entropy change indicates a higher de- calculations for much of chemistry. gree of ordering of solvent molecules in form B than in The valence-bond wave functions have been con- form A. structed using the exact Hamiltonian with simultaneous A rapid equilibrium between ion pairs and free ions (1) This work has been supported by the Chemistry Programs Section cannot explain our observations, as rapid interchanges of the U. S. Atomic Energy Commission Research Division. of different sodium nuclei would broaden out the metal (2) L. C. Allen, R. M. Erdahl, and J. L. Whitten, J. Am. Chem. Soc., splitting. We observe the spectra of the free ion as 87, 3769 (1965). (3) C. K. Jgrgensen, “Inorganic Complexes,” Academic Press Inc., well, showing that a second equilibria between ion pairs New York, N. Y., 1963, p 33. and free ion is present.2 (4) R. M. Noyes, J. Am. Chem. SOC.,85, 2202 (1963). This article also suggests that HeH might be observed. A very precise wave func- (8) J. A. Pople, W. G. Schneider, and H. J. Bernstein, “High Reso- tion leading to a repulsive potential energy curve for this molecule has lution Nuclear Magnetic Resonance,” McGraw Hill Book Co., Inc., been obtained by H. S. Taylor and F. E. Harris, Mol. Phys., 7 , 287 New York, N. Y.,1959, p 222. (1963).
Communications t o the Editor
616 l.OOr assign an effective radius to helium or bond length for
I t H e 0 or HeF (the leading term in the wave functions
effectively represents two neutral atoms repelling one another, and its coefficient measures the extent to which they have achieved a free atom-like behavior). As would be expected, the triatomic bifluorides lie below the diatomic fluorides because their extra symmetry ele- ment leads to resonance. The particularly interesting result showing the oxides to lie lower in energy than the fluorides arises from three factors which together over- ride the greater electronegativity of fluorine. In the neutral states 2s-2p hybridization, favored in oxygen over fluorine because of the smaller orbital energy sep- aration, together with the existence of half-filled 7r orbit- als in the oxygen-containing species permits an energy lowering charge redistribution. Hybridization in these states allows the charge to move away from the be- tween atom-repulsive region. Among the singly ionized states there are three in N e 0 and one in H e 0 which significantly lower the energy through formation of electron-pair bonds between open shells on each atom. Hybridization in the ionic states has the opposite sense to that in the neutral states, favoring the pair bonds by building up the charge between atoms. Purely ionic contributions are almost identical for both the fluorides and oxides, and the doubly ionized states, possible for I I the oxides but not the fluorides, make such an insig- 0.0' 2.b 2.5 3.0 nificant contribution that they have been omitted from BOND LENGTH (otomic units) the approximate wave function tabulation in Table I. Figure 1. Average bond energies vs. bond Iength. In general, binding is discouraged because in the dom- inant states one of the atoms always has a closed-shell configuration. Since H e 0 exhibited the least repulsion, inclusion of all the electrons. A complete configura- an even more elaborate configuration interaction, in- tion interaction over the occupied atomic orbitals was cluding different orbitals for different spins on helium, carried out for each molecule with a Hartree-Fock was carried out with the result shown by the dotted atomic basis set. Thus the N e 0 wave function curve in Figure 1. includes the chemical structures NeO, Ne+O-, Ne2+02-, For argon the one-electron orbital energies of the 3p and is composed of 16 states made up from twenty- and 3s are remarkably close to degeneracy with the 0 2p four 18 X 18 determinants. The curves of Figure 1 and 0 2s, respectively. This renders simple electro- are all singlets with the oxygen atoms going to a 'D negativity arguments ineffective, but our quantitative configuration at infinite separation. Triplet states for numerical experience with neon and helium suggests the oxides were calculated. For these the free oxygen that the strong mixing of these states may produce atom is in its ground-state 3Pconfiguration (calculated minima in the potential energy surfaces for ArOB and to be 0.0805 au lower than the ID), but the molecular Ar04. For these and the fluorides ArF2, and ArF4,it is potential energy curves lie even higher than the corre- decidedly a border-line case as to whether or not they sponding fluorides. Table I displays the chemically will show potential minima, and from a theoretical viewpoint it will require wave functions of the present Table I. Wave Functions at 2.0 au (1.06 A) degree of sophistication to provide a convincing answer. Such calculations are under way in this laboratory. The He0 9 E +0.714He0(2~)~(2p,)~ - 0.072HeO(2~)(2p,)(2p,)~ - present massive synthesis effort for helium, neon-, 0.071He0(2p)6 - 0.051He0(2s)z(2pu)z(2p~)z+ and argon-containing species will provide a rigorous 0.377He+O-(2~)~(2p~)(2p,)~ experimental test of the theory. Ne0 g E +0.600Ne0(2~)~(2p,)~ - O.l57Ne0(2~)(2p,)(2p,)~ - 0.037Ne0(2~)~ - - 0.031NeO(2s)2(2pu)z(2p~)z Leland C. Allen, Arthur R;I. Lesk, Robert M. Erdahl 0.364Nei(2s)2(2p,)(2p,)40~(2s)2(~pu)(~p,)4 - Department of Chemistry, Princeton Uttiversity + O.l07Ne+(2~)(2p)~0-(2s) 2(2pu)(2pT) * Princeton, New Jersey 08540 0.043Ne+(2s)2(2pu)(2p,)40-(2s)(2p)6 Received September 28, 196s HeF P S +O,848HeF(2~)~(2p,)(2p,)~ + 0.282He+F- NeF Yr Ei +0.770MeF(2~)~(2p,)(2p,)~ - Crystal Structure Studies of Some Unusual + 0.360Ne+(2~)~(2p,)(2p,)~F 0.104Ne+(2~)(2p)~F- Antimony Bromide Salts' Sir: significant terms in the wave functions for the various The group of salts of the type RzSbXs (R = NH4+, species. The fact that the neon-associated species lie Rb+, or Cs+; X = C1 or Br) has been the subject of con- above those with helium can be attributed simply to the (1) Contribution No. 1808. This work was performed in the Ames relative size of these atoms, although it is difficult to Laboratory of the U. S. Atomic Energy Commission.
Journal of the American Chemical Society 88:3 February 5, I966