The influence of vibrational and chemical non-equilibrium on the dynamics of velocity gradients and pressure-Hessian tensors is investigated in this study. Such non-equilibrium flows typically occur in high-speed compressible turbulence at elevated temperatures, as observed in reentry vehicles or hypersonic flights. In the first part of the study, we derive the exact evolution equations for the velocity gradients and pressure-Hessian tensors under vibrational and chemical non-equilibrium conditions. We identify the inertial, vibrational, and chemical mechanisms in this evolution equation. In the second part of this study, we focus on assessing the relative importance of these mechanisms across different simulation cases. In this work, we present direct numerical simulations of isotropic decaying turbulence, which consider both vibrational and chemical non-equilibrium effects. It is found that in the presence of chemical and vibrational non-equilibrium, (i) vibrational relaxation processes are expedited in terms of mean and fluctuating flow fields. (ii) Vortical fluctuations increase while dilatational fluctuations are suppressed. (iii) The relative strength of the pressure-Hessian tensor compared to the velocity gradient tensor is reduced. (iv) The explicit effects of vibrational mechanisms on the pressure-Hessian evolution equation are diminished, whereas chemical mechanisms substantially influence the dynamics compared to inertial mechanisms throughout the turbulence decay process. This study highlights the need for robust turbulence closure models for chemical mechanisms to accurately capture the effects of thermal non-equilibrium on the dynamics of velocity gradients in compressible flows.
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