We study the basic mechanisms allowing light to photoswitch at the molecular scale a spin-crossover material from a low- to a high-spin state. Combined femtosecond x-ray absorption performed at LCLS X-FEL and optical spectroscopy reveal that the structural stabilization of the photoinduced high-spin state results from a two step structural trapping. Molecular breathing vibrations are first activated and rapidly damped as part of the energy is sequentially transferred to molecular bending vibrations. During the photoswitching, the system follows a curved trajectory on the potential energy surface.
Using femtosecond time-resolved x-ray diffraction, we directly monitor the coherent lattice dynamics through an ultrafast charge-density-wave-to-metal transition in the prototypical Peierls system K(0.3)MoO(3) over a wide range of relevant excitation fluences. While in the low fluence regime we directly follow the structural dynamics associated with the collective amplitude mode; for fluences above the melting threshold of the electronic density modulation we observe a transient recovery of the periodic lattice distortion. We can describe these structural dynamics as a motion along the coordinate of the Peierls distortion triggered by the prompt collapse of electronic order after photoexcitation. The results indicate that the dynamics of a structural symmetry-breaking transition are determined by a high-symmetry excited state potential energy surface distinct from that of the initial low-temperature state.
Femtosecond time-resolved X-ray diffraction is used to study a photo-induced phase transition between two charge density wave (CDW) states in 1T-TaS2, namely the nearly commensurate (NC) and the incommensurate (I) CDW states. Structural modulations associated with the NC-CDW order are found to disappear within 400 fs. The photo-induced I-CDW phase then develops through a nucleation/growth process which ends 100 ps after laser excitation. We demonstrate that the newly formed I-CDW phase is fragmented into several nanometric domains that are growing through a coarsening process. The coarsening dynamics is found to follow the universal Lifshitz-Allen-Cahn growth law, which describes the ordering kinetics in systems exhibiting a non-conservative order parameter.Among strongly correlated electron systems, superconductors and materials exhibiting metal-insulator transitions are usually characterized by strong electronelectron and electron-phonon couplings [1][2][3]. At thermodynamic equilibrium, the corresponding many-body interactions lead to rich phase diagrams as a function of temperature, pressure or doping. Such compounds also display fascinating out-of-equilibrium physics, in the form of ultra-fast symmetry changes known as photoinduced phase transitions [4][5][6], and occurrence of new, transient states [6][7][8].Charge density wave (CDW) states are broken symmetry states of metals arising from electron-phonon interactions. They are characterized by a periodic modulation of both atomic positions and electron density. The metal-to-CDW phase transition is characterized by the growth of a complex-valued order parameter p = A exp iΦ , which reflects both the amplitude A and the phase Φ of the periodic modulation [3]. A number of photo-induced phase transitions that have been achieved in CDW compounds correspond to a suppression of the CDW order, i.e. a transition between a CDW state and a metallic state free of any structural modulation [5,[9][10][11][12][13][14][15]. Among those, the photo-induced suppression of the CDW state in blue bronze was shown to involve a coherent motion of atoms along the normal coordinates of the CDW amplitude mode [5]. In this case, the amplitude mode allows continuous variations of the modulus of the order parameter |p|, the metallic state corresponding to |p|=0. In the present work, we focus on the photo-induced phase transition between the nearly commensurate (NC) and the incommensurate (I) CDW states in 1T-TaS 2 , which exhibit two distinct order parameters. When thermallyinduced, this first-order phase transition involves a discontinuous change of atomic positions, and a coexistence of NC and I phase domains over a 3 K range [16,17]. It is thus expected that the photo-induced I phase appears through non-coherent atomic motions, by a nucleation/growth process. We report that the photo-induced NC → I phase is completed within 100 ps after laser excitation. At this 100 ps delay, the photo-induced I-CDW phase is found divided into domains with a typical size of 150Å. Its ordering kinet...
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