Probing IR-Raman vibrationally excited molecules with X-ray spectroscopy

► We investigate infrared pump/X-ray probe spectroscopy. ► It is demonstrated to be a powerful tool for exploring molecular bond dissociation. ► With the example of HCl, we show that complete population transfer along the vibrational ladder can be achieved. ► X-ray photoelectron spectrum is a clear signature of the probed vibrational level.