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Over the last 20 years, XUV and X-ray free-electron lasers have enabled a wide variety of time-resolved experiments that have dramatically advanced our understanding of ultrafast molecular dynamics on atomic length scales and femtosecond time scales. This review focuses on experimental studies of ultrafast dynamics of atoms and molecules in the gas phase, tracing the development of the field from early proof-of-principle studies to recent pump-probe experiments that elucidate the coupled electronic and nuclear dynamics during photochemical reactions with a temporal resolution that is now extending into the attosecond domain.
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