Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems.

Abstract

Single-excitation methods, namely, configuration interaction singles and time-dependent density functional theory (TDDFT), along with semiempirical versions thereof, represent the most computationally affordable electronic structure methods for describing electronically excited states, scaling as [Formula: see text] absent further approximations. This relatively low cost, combined with a treatment of electron correlation, has made TDDFT the most widely used excited-state quantum chemistry method over the past 20+ years. Nevertheless, certain inherent problems (beyond just the accuracy of this or that exchange-correlation functional) limit the utility of traditional TDDFT. For one, it affords potential energy surfaces whose topology is incorrect in the vicinity of any conical intersection (CI) that involves the ground state. Since CIs are the conduits for transitions between electronic states, the TDDFT description of photochemistry (internal conversion and intersystem crossing) is therefore suspect. Second, the [Formula: see text] cost can become prohibitive in large systems, especially those that involve multiple electronically coupled chromophores, for example, the antennae structures of light-harvesting complexes or the conjugated polymers used in organic photovoltaics. In such cases, the smallest realistic mimics might already be quite large from the standpoint of ab initio quantum chemistry. This Account describes several new computational methods that address these problems. Topology around a CI can be rigorously corrected using a "spin-flip" version of TDDFT, which involves an α → β spin-flipping transition in addition to occupied → virtual excitation of one electron. Within this formalism, singlet states are generated via excitation from a high-spin triplet reference state, doublets from a quartet, etc. This provides a more balanced treatment of electron correlation between ground and excited states. Spin contamination is problematic away from the Franck-Condon region, but we describe a "spin-complete" version of the theory in which proper spin eigenstates are obtained by construction. For systems of coupled chromophores, we have developed an ab initio version of the Frenkel-Davydov exciton model in which collective excitations of the system are expanded in a basis of excited states computed for individual chromophores. The monomer calculations are trivially parallelizable, as is computation of the coupling matrix elements needed to construct the exciton Hamiltonian, and systems containing hundreds of chromophores can be tackled on commodity hardware. This enables calculations on organic semiconductors, where even small model systems exhibit a semicontinuum of excited states that renders traditional TDDFT computationally challenging. Despite including only single excitations on each monomer, the exciton model can describe entangled spins on two or more monomers, an effect that is responsible for excitation energy transfer between chromophores, for example, in singlet fission. Excitonic approximations can also be applied to the TDDFT equations themselves, and a particularly promising application is to describe the effects of environment on an excitation that is localized on a single chromophore. This "local excitation approximation" to TDDFT allows an essentially arbitrary number of solvent molecules to be included in the calculation in a highly parallelizable way such that the time-to-solution increases only very slowly as additional solvent molecules are added. It is therefore possible to converge the calculation with respect to describing an ever-larger portion of the environment at a quantum-mechanical level.