Dynamical Simulations of Carotenoid Photoexcited States Using Density Matrix Renormalization Group Techniques

[Image: see text] We present a dynamical simulation scheme to model the highly correlated excited state dynamics of linear polyenes. We apply it to investigate the internal conversion processes of carotenoids following their photoexcitation. We use the extended Hubbard-Peierls model, [Image: see text], to describe the π-electronic system coupled to nuclear degrees of freedom. This is supplemented by a Hamiltonian, [Image: see text], that explicitly breaks both the particle-hole and two-fold rotation symmetries of idealized carotenoid structures. The electronic degrees of freedom are treated quantum mechanically by solving the time-dependent Schrödinger equation using the adaptive time-dependent DMRG (tDMRG) method, while nuclear dynamics are treated via the Ehrenfest equations of motion. By defining adiabatic excited states as the eigenstates of the full Hamiltonian, [Image: see text], and diabatic excited states as eigenstates of [Image: see text], we present a computational framework to monitor the internal conversion process from the initial photoexcited 1(1)B(u)(+) state to the singlet triplet-pair states of carotenoids. We further incorporate Lanczos-DMRG to the tDMRG-Ehrenfest method to calculate transient absorption spectra from the evolving photoexcited state. We describe in detail the accuracy and convergence criteria for DMRG, and show that this method accurately describes the dynamical processes of carotenoid excited states. We also discuss the effect of the symmetry-breaking term, [Image: see text], on the internal conversion process, and show that its effect on the extent of internal conversion can be described by a Landau–Zener-type transition. This methodological paper is a companion to our more explanatory discussion of carotenoid excited state dynamics in Manawadu, D.; Georges, T. N.; Barford, W. Photoexcited State Dynamics and Singlet Fission in Carotenoids. J. Phys. Chem. A2023, 127, 1342.