One of the central problems in quantum theory is to characterize, detect, and quantify quantumness in terms of classical strategies. Dephasing processes, caused by non-dissipative information exchange between quantum systems and environments, provides a natural platform for this purpose, as they control the quantum-to-classical transition. Recently, it has been shown that dephasing dynamics itself can exhibit (non)classical traits, depending on the nature of the system-environment correlations and the related (im)possibility to simulate these dynamics with Hamiltonian ensembles---the classical strategy. Here we establish the framework of detecting and quantifying the nonclassicality for pure dephasing dynamics. The uniqueness of the canonical representation of Hamiltonian ensembles is shown, and a constructive method to determine the latter is presented. We illustrate our method for qubit, qutrit, and qubit-pair pure dephasing and describe how to implement our approach with quantum process tomography experiments. Our work is readily applicable to present-day quantum experiments.
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