The TSH methodology is based on Tully's fewest switches 48 a three-step propagator technique, and local diabatisation. The simulations utilise the diagonal electronic basis, which is obtained by diagonalisation of the LVC potential matrix defined in Equations 1 and 2 in the Supplementary Information. We used a time step of 0.5 fs and 0.005 fs for the nuclear and electronic propagation, respectively. 1000 initial conditions were sampled from a ground-state Wigner distribution, which were filtered using a stochastic algorithm accounting for conditions of the excitation process, i.e., excitation energies and oscillator strengths. We utilised a 0.1 eV wide energy window centered at 2.358 eV, which is the excitation energy of the lowest-lying optically-active 1 MLCT state at the FC geometry. This process resulted in 716 selected initial conditions, from which we propagated the corresponding trajectories for 1.5 ps time duration. We used the energy-based method of Granucci et al. to correct electronic decoherence effects utilising a decoherence parameter of 0.1 a.u. The number of trajectories (716) ensured convergence of the simulated excitedstate dynamics. The difference X-ray scattering signal ∆S(t) = S(t)-S(0) was calculated by evaluating the Debye equation for each structure and averaging over all trajectories. The TSH dynamics simulations were performed using the SHARC2.1 software.