Symmetry breaking across phase transitions often causes changes in selection rules and emergence of optical modes which can be detected via spectroscopic techniques or generated coherently in pump-probe experiments. In second-order or weakly first-order transitions, fluctuations of the order parameter are present above the ordering temperature, giving rise to intriguing precursor phenomena, such as critical opalescence. Here, we demonstrate that in magnetite (Fe 3 O 4 ) light excitation couples to the critical fluctuations of the charge order and coherently generates structural modes of the ordered phase above the critical temperature of the Verwey transition. Our findings are obtained by detecting coherent oscillations of the optical constants through ultrafast broadband spectroscopy and analyzing their dependence on temperature. To unveil the coupling between the structural modes and the electronic excitations, at the origin of the Verwey transition, we combine our results from pump-probe experiments with spontaneous Raman scattering data and theoretical calculations of both the phonon dispersion curves and the optical constants. Our methodology represents an effective tool to study the real-time dynamics of critical fluctuations across phase transitions.

In systems having an anisotropic electronic structure, such as the layered materials graphite, graphene and cuprates, impulsive light excitation can coherently stimulate specific bosonic modes, with exotic consequences for the emergent electronic properties. Here we show that the population of E2g phonons in the multiband superconductor MgB2 can be selectively enhanced by femtosecond laser pulses, leading to a transient control of the number of carriers in the σ-electronic subsystem. The nonequilibrium evolution of the material optical constants is followed in the spectral region sensitive to both the a-and c-axis plasma frequencies and modeled theoretically, revealing the details of the σ-π interband scattering mechanism in MgB2.

We present inelastic neutron scattering data across the Verwey transition in magnetite, obtained for a single crystal via a detwinning method. We provide direct evidence of the influence of the charge order on the transverse-acoustic phonons, associated with discontinuous hardening and narrowing at the transition temperature, and energy splitting for different polarizations. This contrasts with the behavior of the transverse-optical X 3 mode, which does not present any critical anomaly, contrary to theoretical expectations. Our data indicate that the incommensurate fluctuations occurring above the critical temperature become locked to the lattice at the transition point, through a mechanism similar to the crystallization of a two-dimensional liquid on a solid surface. Our results also contribute to clarify the different dynamics and mutual interactions of the electronic and structural modes in the Verwey transition.

We present inelastic light scattering data on a single crystal of magnetite (Fe 3 O 4) across the Verwey transition. We identify anomalies of the lattice vibrations that originate from strong coupling to electronic excitations. We reveal spectroscopic signatures of diffusive modes in the electronic contribution to the Raman response function. We thereby provide information on the critical dynamics and the hierarchy of the structural and electronic modes in the mechanism of the Verwey transition.

A femtosecond pump-probe setup is described that is optimised for broadband transient reflectivity experiments on solid samples over a wide temperature range. By combining high temporal resolution and a broad detection window, this apparatus can investigate the interplay between coherent collective modes and high-energy electronic excitations, which is a distinctive characteristic of correlated electron systems. Using a single-shot readout array detector at frame rates of 10 kHz allows resolving coherent oscillations with amplitudes <10−4. We demonstrate its operation on the charge-transfer insulator La2CuO4, revealing coherent phonons with frequencies up to 13 THz and providing access into their Raman matrix elements.