Graph-Covariant Bottom-Up Scale-Bridging Reconstruction of Ground and Excited States of Extended Systems

Abstract

We propose a hierarchical scale-bridging construction for building first principles electronic structure models of extended molecular aggregates with disorder, and its practical realization in exciton systems. The general construction, referred here as to the encapsulation, is based on a recursive operator-valued hierarchy cast in a dual graph-theoretic (discrete) and configuration-space (continuous) structure, in which variables associated with a coarser level parameterize operators governing the degrees of freedom at the next finer level in a graph-covariant, geometry-preserving fashion. In an exemplary application of this scheme, aggregate-level ground- and excited-state operators are constructed through a many-body expansion (MBE), with matrix elements evaluated in a basis comprising the aggregate ground state and local Frenkel excitations. The required monomer and dimer building blocks are obtained from DFT and TDDFT calculations, yielding aggregate-level 1-particle transition density matrices as well as Hamiltonian, dipole moment and other operators that can be evaluated at the level of the building blocks. Starting from structural models obtained from experiment or molecular dynamics, this approach generates aggregate-level operators in a bottom-up fashion without fitting parameters to spectroscopic data or performing calculations on larger system cutouts. A numerical demonstration is given for an excitonic manifold in crystalline quaterthiophene. In particular, through its intrinsic configuration-dependence encoded in the encapsulations, it will provide a bridge between static electronic structure calculations for realistic, structurally disordered aggregates and quantum or quantum-classical simulations of exciton-vibrational dynamics.