Attosecond Probing of Coherent Vibrational Dynamics in CBr4.

A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a₁) mode of CBr₄, by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 10¹² W/cm². Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M_4,5 3d_3/2,5/2 edges around 70 eV. The results are augmented by nuclear time-dependent Schrödinger equation simulations. Slopes of the (Br 3d_3/2,5/2)^-110a₁* core-excited state potential energy surface (PES) along the a₁ mode are calculated to be -9.4 eV/Å from restricted open-shell Kohn-Sham calculations. Using analytical relations derived for the small-displacement limit and the calculated slopes of the core-excited state PES, a deeper insight into the vibrational dynamics is obtained by retrieving the experimental excursion amplitude of the vibrational wavepacket and the amount of population transferred to the vibrational first-excited state as a function of pump-pulse peak intensity. Experimentally, the results show that XUV ATAS is capable of resolving oscillations in the XUV absorption energy on the order of a few to tens of meV with tens of femtosecond time precision. This corresponds to change in C-Br bond length on the order of 10^-4 to 10^-3 Å. The results and the analytic relationships offer a clear physical picture, on multiple levels of understanding, of how the pump-pulse peak intensity controls the vibrational dynamics launched by nonresonant ISRS in the small-displacement limit.