Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene

Morrison, Adrian F.; Herbert, John M.

doi:10.1063/1.4985607

Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene

Journal Article · Wed Jun 14 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4985607· OSTI ID:1604464

Morrison, Adrian F. ^[1]; ^[2]

The Ohio State Univ., Columbus, OH (United States); The Ohio State University
The Ohio State Univ., Columbus, OH (United States)

Recently, we introduced an ab initio version of the Frenkel-Davydov exciton model for computing excited-state properties of molecular crystals and aggregates. Within this model, supersystem excited states are approximated as linear combinations of excitations localized on molecular sites, and the electronic Hamiltonian is constructed and diagonalized in a direct-product basis of non-orthogonal configuration state functions computed for isolated fragments. In this work, we derive and implement analytic derivative couplings for this model, including nuclear derivatives of the natural transition orbital and symmetric orthogonalization transformations that are part of the approximation. Nuclear derivatives of the exciton Hamiltonian’s matrix elements, required in order to compute the nonadiabatic couplings, are equivalent to the “Holstein” and “Peierls” exciton/phonon couplings that are widely discussed in the context of model Hamiltonians for energy and charge transport in organic photovoltaics. As an example, we compute the couplings that modulate triplet exciton transport in crystalline tetracene, which is relevant in the context of carrier diffusion following singlet exciton fission.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008550; SC0008850

OSTI ID:: 1604464

Alternate ID(s):: OSTI ID: 1363833

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 146; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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