(a) Experimental and calculated transient Cr L3-edge
absorption difference spectra of Cr(CO)6 in octane solution.
Calculations are performed at the RASSCF level of theory. Difference
spectra of the Cr(CO)5-alkane σ-complex and the Cr(CO)5 fragment are generated with respect to Cr(CO)6 (spectrum of the respective species minus spectrum of Cr(CO)6). For better comparison, the depletion of the calculated
Cr(CO)5-alkane difference spectra is scaled to match the
depletion of the experimental spectrum, and the Cr(CO)5 difference spectrum is scaled accordingly. The experimental steady-state
spectrum is additionally shown for comparison and scaled to match
the amplitude of the depletion of the transient difference spectra.
(b) Calculated L3-edge absorption spectrum of Cr(CO)6, the Cr(CO)5-alkane σ-complex, and the Cr(CO)5 fragment. The maximum of the Cr(CO)6 spectrum
is scaled to 1, and the other spectra are scaled accordingly. The
inset shows a close-up of the transient pre-edge region between 573.1
and 575.75 eV. (c) Pump–probe delay traces measured at the
energies indicated in (a). The delay traces are modeled with a step
function broadened by a Gaussian function.