The isotope effect and excitation-energy dependence have been measured in the oxygen $K$-edge x-ray emission spectrum (XES). The use of XES to monitor core decay processes provides information about molecular dynamics (MD) on an ultrafast time scale through the O$1s$ lifetime of a few femtoseconds. Different nuclear masses give rise to differences in the dynamics and the observed isotope effect in XES is direct evidence of the importance of such processes. MD simulations show that even the excitation-energy dependence in the XES is mainly related to differences in core-excited-state dynamics.

• Received 9 November 2004

DOI:https://doi.org/10.1103/PhysRevLett.94.227401