Fig. 5
Quantitative interpretation of the time dependence of three selected photoelectron bands. a–c Influence of the bond angle Θ on the local Ip, where b, c display the potential energy curves of the neutral states and the cationic states, respectively, and a shows the vertical Ip highlighting the selected photoelectron bands (see Fig. 4d). The color code corresponds to b distinguishing transitions from the lower adiabatic state (solid lines) and transitions from the upper adiabatic state (dashed lines). Diamond markers indicate LAPE contributions. The vertical dashed black line in a indicates the CI. d–f show the dependence of the bond distance r1. The gray curve in f indicates the complete upper adiabatic state, while the dashed black line emphasizes the accessible part of this state (see text). g Calculated mean band variation (see Fig. 4e). h–j Comparison of experimental data with the rescaled calculated traces. The shaded regions represent the standard deviation of the mean, obtained from 20 consecutive measurements. Contributions from the individual states are displayed using the color code from a, d. The additional green line in i shows the contribution of the three triplet states, i.e., from large amplitude motion, its peak at 72 fs is highlighted by an arrow. The arrow in j indicates the peak contribution of the signal associated with the CI region of the nuclear configuration space at 36 fs
