"Dynamics of the OH Stretching Mode in Crystalline Ba(ClO4)2·3H2O"D. Hutzler, Ch. Brunner, P. Petkov, T. Heine, S. Fischer, E. Riedle, R. Kienberger, and H. Iglev
J. Chem. Phys. 148, 054307 (2018).
The vibrational dynamics of theOHstretching mode in Ba(ClO4)2 trihydrate are investigated by means
of femtosecond infrared spectroscopy. The sample offers plane cyclic water trimers in the solid phase
that feature virtually no hydrogen bond interaction between thewater molecules. Selective excitation of
the symmetric and asymmetric stretching leads to fast population redistribution, while simultaneous
excitation yields quantum beats, which are monitored via a combination tone that dominates the
overtone spectrum. The combination of steady-state and time-resolved spectroscopy with quantum
chemical simulations and general theoretical considerations gives indication of various aspects of
symmetry breakage. The system shows a joint population lifetime of 8 ps and a long-lived coherence
between symmetric and asymmetric stretching, which decays with a time constant of 0.6 ps.
BMO authors (in alphabetic order):