Photofragmentation of cyclobutanone at 200 nm: TD-DFT vs CASSCF electron diffraction (2401.07597v2)

Abstract: To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strenghts. Twelve singlet and twelve triplet states are treated using TD-B3LYP-D3/6-31+G$^{**}$ for the electronic structure and the nuclei are propagated with the Tully Surface Hopping method. Using TD-DFT, we are able to predict the bond cleavage that takes place on the S$_1$ surface as well as the ultrafast deactivation from the Rydberg n-3s state to the n$\pi^*$. After showing that triplet states and higher-lying singlet states do not play any crucial role during the early dynamics (i.e., the first 300 fs), the SA(6)-CASSCF(8,11)/aug-cc-pvDZ method is used as an electronic structure and the outcome of the non-adiabatic dynamic simulations is recomputed. Gas-phase ultrafast electron diffraction (GUED) spectra are computed for both electronic structure methods, showing significantly different results.