The Role of Double Excitations in Exciton Dynamics of Multiazobenzenes: Trisazobenzenophane as a Test Case.

Molecular exciton dynamics underlie energy and charge transfer processes in organic multichromophoric systems. A particularly interesting class of the latter is multiphotochromic systems made of molecules capable of photochemical transformations. Exciton dynamics in assemblies of photoswitches have been recently investigated using either the molecular exciton model or supermolecular configuration interaction (CI) singles, both approaches being based on a semiempirical Hamiltonian and combined with surface hopping molecular dynamics. Here, we study how inclusion of double excitations in nonadiabatic dynamics simulations affects exciton dynamics of multiazobenzenes, using trisazobenzenophane as an example. We find that both CI singles and CI singles and doubles yield virtually the same time scale of dynamical exciton localization, ∼50 fs for the studied multiazobenzene. However, inclusion of double excitations considerably affects the excited state lifetimes and isomerization quantum yields.