Intersystem crossing and internal conversion dynamics with GAIMS-TeraChem: Excited state relaxation in 2-cyclopentenone

Excited states relaxation in complex molecules often involves two types of nonradiative transitions, internal conversion (IC) and intersystem crossing (ISC). In the situations when the timescales of IC and ISC are comparable, an interplay between these two types of transitions can lead to complex nonadiabatic dynamics on multiple electronic states of different characters and spin multiplicities. We demonstrate that the generalized ab initio multiple spawning (GAIMS) method interfaced with the fast graphics processing unit-based TeraChem electronic structure code can be used to model such nonadiabatic dynamics involving both the IC and ISC transitions in molecules of moderate size. We carried out 1500 fs GAIMS simulations leading to the creation of up to 2500 trajectory basis functions to study the excited states relaxation in 2-cyclopentenone. After a vertical excitation from the ground state to the bright S-2 state, the molecule quickly relaxes to the S-1 state via conical intersection. The following relaxation proceeds along two competing pathways: one involves IC to the ground state, and the other is dominated by ISC to the low-lying triplet states. The time constants describing the population transfer between the six lowest singlet and triplet states predicted by the GAIMS dynamics are in good agreement with the characteristic times of IC and ISC obtained from the analysis of the time-resolved photoelectron spectrum.

Automated summary

In excited states relaxation, internal conversion and intersystem crossing are crucial nonradiative transitions, whose interplay can lead to complex nonadiabatic dynamics. By utilizing the GAIMS method with TeraChem, nonadiabatic dynamics involving internal conversion and intersystem crossing transitions in moderate-sized molecules can be effectively modeled. The time constants describing the population transfer between different electronic states predicted by the GAIMS dynamics align well with characteristic times obtained from the analysis of the time-resolved photoelectron spectrum.