Location of the H atoms in ammonium persulphate by deuteron NMR. Verification by X-ray diffraction

It is demonstrated that H atoms can be located by the spectroscopic method of deuteron NMR. The requirement is that the 'heavy-atom' positions are known from diffraction studies. The technique allows an accuracy of the order of 0.01 A. The compound studied is ammonium persulphate (APS), (NH(4))(2)S(2)O(8). APS crystallizes in space group P2(1)/n with lattice parameters a = 6.1340 (2), b = 7.9324 (3), c = 7.7541 (3) A and beta = 94.966 (1) degrees at T = 118 K. In perdeuterated crystals of APS, only one of the deuterons of every ND(4)(+) ion becomes localized at low temperatures. Therefore, most of this work uses samples with 9% deuteration. In such crystals, most of the ammonium ions containing deuterons come in the form of NDH(3)(+) ions. At T < 25 K, the single deuteron of these ions becomes localized in one of four equilibrium sites. The deuteron site occupancies differ from each other and are measured at 17 K. The deuterons are located in three steps. (i) The deuteron quadrupole-coupling (QC) tensors are measured at 17 K. Their unique principal directions are identified, as is well justified, with the N-D bond directions. (ii) The fine structure of a deuteron NMR line is analyzed in terms of the magnetic dipole-dipole interactions between all nuclei in an NDH(3)(+) ion to obtain the N-D and D-H internuclear distances. (iii) An empirical relation between deuteron QC constants and D.O distances in N-D.O hydrogen bonds is exploited to assign the N-D bond vectors to the appropriate N atom of which there are four in the unit cell. The results are highly relevant for an understanding of the complex tunnelling and stochastic reorientation dynamics of the ammonium ions in APS. They are verified by a complementary X-ray diffraction study