Phonon-mediated path-interference in electronic energy transfer

Hossein-Nejad, Hoda; Olaya-Castro, Alexandra; Scholes, Gregory D.

doi:doi:10.1063/1.3675844

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Nonspherical model density matrices for Rung 3.5 density functionals

“Rung 3.5” exchange-correlation functionals for Kohn-Sham density functional theory depend linearly on the nonlocal one-particle density matrix of the noninteracting Kohn-Sham reference system. Rung 3.5 functionals also require a semilocal model for the one-particle density matrix. This work presents new model density matrices for Rung 3.5 functionals. The resulting functionals give reasonable predictions for total energies, molecular thermochemistry and kinetics, odd-electron bonds, and conjuga...

A new fragment-based approach for calculating electronic excitation energies of large systems

We present a new fragment-based scheme to calculate the excited states of large systems without necessity of a Hartree-Fock (HF) solution of the whole system. This method is based on the implementation of the renormalized excitonic method [M. A. Hajj et al., Phys. Rev. B 72, 224412 (2005)10.1103/PhysRevB.72.224412] at ab initio level, which assumes that the excitation of the whole system can be expressed by a linear combination of various local excitations. We decomposed the whole system into se...

We present a formalism to quantify the contribution of path-interference in phonon-mediated electronic energy transfer. The transfer rate between two molecules is computed by considering the quantum mechanical amplitudes associated with pathways connecting the initial and final sites. This includes contributions from classical pathways, but also terms arising from interference of different pathways. We treat the vibrational modes coupled to the molecules as a non-Markovian harmonic oscillator bath, and investigate the correction to transfer rates due to the lowest-order interference contribution. We show that depending on the structure of the harmonic bath, the correction due to path-interference may have a dominant vibrational or electronic character, and can make a notable contribution to the transfer rate in the steady state.

Article Outline

INTRODUCTION
THEORETICAL METHODOLOGY
1. Kenkre and Knox revisited
2. Manipulation of probabilities: Sequential versus superexchange
3. Linear exciton-phonon Hamiltonian
4. Pathway associated memory kernels
RESULTS AND DISCUSSION
1. First-order interference in PE545
  1. Single mode spectral density
  2. Brownian oscillator spectral density
2. Path-interference correction: Short time versus steady state
3. Classical limit
4. Higher order pathways
5. Comparison to other treatments
CONCLUSION

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KEYWORDS and PACS

Keywords

harmonic oscillators, phonons, vibrational states

PACS

33.15.Mt

Rotation, vibration, and vibration-rotation constants
33.20.Tp

Vibrational analysis
36.20.Ng

Vibrational and rotational structure, infrared and Raman spectra

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http://dx.doi.org/10.1063/1.3675844

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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