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We consider the Cauchy problem for the defocusing nonlinear Schrödinger (NLS) equation with step-like initial data. Using the nonlinear steepest descent method, we derive the long-time asymptotic expansion of the solution to the Cauchy problem in three distinct transition regions. In the first two transition regions, the leading-order asymptotics are characterized by Painlevé \uppercase\expandafter{\romannumeral34\relax}-type formula, while in the third one is a collisionless shock region, the leading-order asymptotics is describedin terms of Riemann theta functions. Our analysis is based on the Riemann-Hilbert formulation associated with the Cauchy problem of the defocusing NLS equation.

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