Fig. 5: Nuclear motion effect of spatial delocalization in attosecond photoemission time delays.
From: Attosecond delays between dissociative and non-dissociative ionization of polyatomic molecules
a Calculated relative photoemission delays between the dissociative (\({{{{{{{{\rm{CH}}}}}}}}}_{3}^{+}/{{{{{{{\rm{H}}}}}}}}\)) and non-dissociative channel (\({{{{{{{{\rm{CH}}}}}}}}}_{4}^{+}\)) as a function of the photon energy, obtained from the complete calculation, \({\tau }_{{{{{{{{\rm{theo}}}}}}}}}^{{{{{{{{{\rm{CH}}}}}}}}}_{3}^{+}/{{{{{{{\rm{H}}}}}}}}}-{\tau }_{{{{{{{{\rm{theo}}}}}}}}}^{{{{{{{{{\rm{CH}}}}}}}}}_{4}^{+}}\) (green squares, same as in Fig. 3a), from only considering the dominant partial wave l = 2, \({\tau }_{l=2}^{{{{{{{{{\rm{CH}}}}}}}}}_{3}^{+}/{{{{{{{\rm{H}}}}}}}}}-{\tau }_{l=2}^{{{{{{{{{\rm{CH}}}}}}}}}_{4}^{+}}\) (cyan circles), from the difference between the corresponding one-photon Wigner time delays, \({\tau }_{{{{{{{{\rm{wig}}}}}}}}}^{{{{{{{{{\rm{CH}}}}}}}}}_{3}^{+}/{{{{{{{\rm{H}}}}}}}}}-{\tau }_{{{{{{{{\rm{wig}}}}}}}}}^{{{{{{{{{\rm{CH}}}}}}}}}_{4}^{+}}\) (grey line), and from the difference between the corresponding one-photon Wigner time delays but only considering the 3a1 channel, \({\tau }_{{{{{{{{\rm{wig}}}}}}}},3{a}_{1}}^{{{{{{{{{\rm{CH}}}}}}}}}_{3}^{+}/{{{{{{{\rm{H}}}}}}}}}-{\tau }_{{{{{{{{\rm{wig}}}}}}}},3{a}_{1}}^{{{{{{{{{\rm{CH}}}}}}}}}_{4}^{+}}\) (orange curve). The latter two delay differences have been evaluated as an average over vibrational and dissociative states (see SM). The right panel shows the electron density distribution of the 3a1 orbital along the C-H bond stretching from 1.1 Å to 2.5 Å in C3v symmetry. b Photoionization delays of SB12-20, l = 2, for ionization from the 3a1 or 1e orbitals, as a function of the C-H internuclear separation. The orange-shaded area indicates the Frank-Condon region. c Symmetry-resolved Franck-Condon factors as a function of the photon energy.
