In azobenzene, manifold I contains a single state S 1 and manifold II consists of 4 states, from S 2 to S 5 . In PSB4, manifold I also contains a single state S 1 and manifold II contains 6 states, from S 2 to S 7 . 100 BOMD trajectories on the S 0 state were run up to 200 fs in the simulation of the GSB cold signal. Other 100 trajectories starting from the S 1 state were propagated to simulate the hot GSB, SE, and ESA signals. We chose snapshots per 10 steps from every trajectory to obtain the vertical excited energies (VEEs) and TDMs.