Proton-transfer dynamics in the hydrogen bond. Inelastic neutron scattering, infrared and Raman spectra of KH(CF 3COO) 2 and CsH(CF 3COO) 2

Abstract

Inelastic neutron scattering (INS), infrared and Raman spectra of potassium and cesium hydrogen bistrifluoroacetate (KH(CF 3COO) 2 and CsH(CF 3COO) 2, respectively) at 20 K are reported. In both crystals H(CF 3COO) 2 − centrosymmetric dimers are linked by strong hydrogen bonds, whose lengths are 2.435 and 2.38 Å, respectively. The principal OH modes appear at the same frequencies for both compounds. The OH stretching band shapes are similar in infrared and in INS. The submaxima are attributed to interactions with other internal modes. Below 200 cm −1, the cesium salt shows three narrow bands which emerge from the density-of-states. They are assigned to localized modes involving the proton. A sharp band at 87 cm −1 corresponds to the “tunnelling” transition in a quasi-symmetric double-minimum potential with a barrier height of 1340 cm −1. The other two narrow bands, at 36 and 49 cm −1, are assigned to the internal torsions of coupled CF 3COO groups. Potential barriers are estimated. A detailed band-shape analysis of the OH bending modes provides clear indications of different dynamics for the two salts. KH(CF 3COO) 2 is rather stiff and phonon wings involving the whole lattice density-of-states are observed for the δOH mode but not for the γOH mode. For this latter, the observed combinations indicate a dynamical coupling with the internal torsion. CsH(CF 3COO) 2 is rather soft and recoil occurs. The INS intensities of the OH bending modes are decreased by Debye-Waller factors and their frequencies are shifted upwards. The estimated masses of the recoiling particles are consistent with strong dynamical coupling of the γOH with the torsional mode on the one hand, and of the δOH with translational modes on the other. The polarizability of the counter ion appears to play a leading role in proton dynamics.