As the evolution of the electronic structure is ultimately responsible for the changes undergone in the solvent, we will first analyze the electronic population dynamics after photoexcitation, to understand which states are populated during the relaxation process. Figure shows the time-resolved adiabatic populations of the considered electronic states. Initially, the singlet population is dominated by the S 3 state. As the overall singlet population decreases, the proportions gradually shift, with the S 2 and then S 1 becoming relatively more prominent due to nonradiative decay. Efficient intersystem crossing (ISC) occurs within the first 1000 fs, resulting in about 90% of the population moving to the triplet manifold, distributed among the three lowest triplet states. At the end of the propagation time, 6% of the population remains in the singlet state (mostly S 1 ); this outcome is referred to as "cold" singlet state (of MLCT character) in the kinetic model below. The total population transfer between singlet and triplet states is summarized in Fig. , together with a biexponential fit that takes into account this "cold" singlet. The total singlet population depletes quickly with a time constant τ = 211 ± 4 fs from the 1 MLCT states, and no 1 MC population is observed. The time constant is in excellent agreement with previous TDDFT-based QM/MM simulations, which provided a 210 ± 20 fs ISC time constant.