We present a theoretical approach for the simulation of time-resolved harmonic spectra, including the effect of nuclear dynamics, which is applicable to complex systems involving many nuclear degrees of freedom. The method is based on the combination of our semiclassical field-induced surface hopping approach for the treatment of laser-induced nuclear dynamics with the time-dependent density functional theory for electron dynamics. We apply our method to the simulation of ultrafast nonadiabatic dynamics and time-resolved harmonic spectra in small silver clusters (Ag${}_2$ and Ag${}_8$), which exhibit discrete molecularlike electronic transitions. We demonstrate that the harmonic signal is highly sensitive to the nuclear dynamics and thus can be used as a probe of coupled electron-nuclear dynamics, which is complementary to common pump-probe methods such as time-resolved photoelectron spectroscopy. Our simulations allowed us also to determine the mechanism and the time scale of nonradiative relaxation in the “magic” Ag${}_8$ cluster and have provided a fundamental insight into ultrafast dynamics of metal nanoclusters in the size regime where “each atom counts.” The excited-state dynamics of Ag${}_8$ involves an isomerization process from the initial structure with $T_{\mathrm{d}}$ symmetry to the quadratic antiprism structure with $D_{4\mathrm{d}}$ symmetry which takes place on a time scale of $~$600 fs and is clearly identified in a time-resolved harmonic signal. Our theoretical approach is generally applicable for the prediction of time-resolved harmonic spectra in complex systems with many nuclear degrees freedom and should serve to stimulate new ultrafast experiments utilizing harmonic signals as a probe for nonadiabatic processes in molecular systems.

• Received 19 November 2010

DOI:https://doi.org/10.1103/PhysRevA.83.033408