Model Hamiltonian analysis of singlet fission from first principles

Shane M. Parker, Tamar Seideman, Mark A Ratner, Toru Shiozaki

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

We present an approach to accurately construct the few-state model Hamiltonians for singlet fission processes on the basis of an ab initio electronic structure method tailored to dimer wave functions, called an active space decomposition strategy. In this method, the electronic structure of molecular dimers is expressed in terms of a linear combination of products of monomer states. We apply this method to tetracene and pentacene, using monomer wave functions computed by the restricted active space (RAS) method. Near-exact wave functions are computed for π-electrons of dimers that contain up to 7 × 1012 electronic configurations. Our product ansatz preserves the diabatic picture of the minimal dimer model, allowing us to accurately identify model Hamiltonians. The wave functions obtained from the model Hamiltonians account for more than 99% of the total wave functions. The resulting model Hamiltonians are shown to be converged with respect to all the parameters in the model, and corroborate previously reported coupling strengths.

Original languageEnglish
Pages (from-to)12700-12705
Number of pages6
JournalJournal of Physical Chemistry C
Volume118
Issue number24
DOIs
Publication statusPublished - Jun 19 2014

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Hamiltonians
fission
Wave functions
Dimers
wave functions
dimers
Electronic structure
monomers
Monomers
electronic structure
products
Decomposition
decomposition
Electrons
configurations
electronics
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Model Hamiltonian analysis of singlet fission from first principles. / Parker, Shane M.; Seideman, Tamar; Ratner, Mark A; Shiozaki, Toru.

In: Journal of Physical Chemistry C, Vol. 118, No. 24, 19.06.2014, p. 12700-12705.

Research output: Contribution to journalArticle

Parker, Shane M. ; Seideman, Tamar ; Ratner, Mark A ; Shiozaki, Toru. / Model Hamiltonian analysis of singlet fission from first principles. In: Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 24. pp. 12700-12705.
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