Free electrons provide a powerful tool for probing material properties at atomic resolution. Recent advances in ultrafast electron microscopy enable the manipulation of free-electron wave functions using laser pulses. It would be of great importance if one could combine the spatial resolution of electron microscopes with the ability of laser pulses to probe coherent phenomena in quantum systems. To this end, we propose a novel concept that leverages free electrons that are coherently shaped by laser pulses to measure quantum coherence in materials. We develop the quantum theory of interactions between shaped electrons and arbitrary qubit states in materials, and show how the postinteraction electron energy spectrum enables measuring the qubit state (on the Bloch sphere) and the decoherence or relaxation times (T_{2}/T_{1}). Finally, we describe how such electrons can detect and quantify superradiance from multiple qubits. Our scheme can be implemented in ultrafast transmission electron microscopes (UTEM), opening the way toward the full characterization of the state of quantum systems at atomic resolution.
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