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When using dimethyl ether (DME) to fuel diesel engines at high load and speed, applying high amounts of exhaust gas recirculation (EGR) to limit NOX emissions, carbon monoxide (CO) emissions are generally high. To address this issue, the combustion and emission processes in such engines were analyzed with the three-dimensional CFD KIVA3V code. The combustion sub-mechanism (76 species and 375 reactions) was validated by comparing simulated ignition delays and flame velocities to reference data under diesel-like and atmospheric conditions, respectively. In addition, simulated and experimentally determined rate of heat release (RoHR) curves and emission data were compared for a heavy-duty single-cylinder DME engine (displaced volume, 2.02 liters) with DME-adapted piston and nozzle geometries. The simulated RoHR curves captured the main features of the experimentally measured curves, but deviated in the premixed (higher peak) and late combustion phases (too high).