### Abstract

Simulation of charge transport in organic semiconducting materials requires the development of strategies for very fast yet accurate estimation of electronic coupling matrix elements for electron transfer between organic molecules (transfer integrals, H_{ab}). A well-known relation that is often exploited for this purpose is the approximately linear dependence of electronic coupling with respect to the overlap of the corresponding diabatic state wave functions for a given donor-acceptor pair. Here we show that a single such relation can be established for a large number of different pi;-conjugated organic molecules. In our computational scheme the overlap of the diabatic state wave function is simply estimated by the overlap of the highest singly occupied molecular orbital of donor and acceptor, projected on a minimum valence shell Slater-type orbital (STO) basis with optimized Slater decay coefficients. After calibration of the linear relation, the average error in H_{ab} as obtained from the STO orbital overlap is a factor of 1.9 with respect to wave function-theory validated DFT calculations for a diverse set of pi;-conjugated organic dimers including small arenes, arenes with S, N, and O heteroatoms, acenes, porphins, and buckyballs. The crucial advantage of the scheme is that the STO orbital overlap calculation is analytic. This leads to speedups of 6 orders of magnitude with respect to reference DFT calculations, with little loss of accuracy in the regime relevant to charge transport in organics.

Original language | English |
---|---|

Pages (from-to) | 4653-4660 |

Number of pages | 8 |

Journal | Journal of Chemical Theory and Computation |

Volume | 10 |

Issue number | 10 |

DOIs | |

Publication status | Published - Oct 14 2014 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Computer Science Applications

### Cite this

*Journal of Chemical Theory and Computation*,

*10*(10), 4653-4660. https://doi.org/10.1021/ct500527v

**Ultrafast estimation of electronic couplings for electron transfer between pi;-conjugated organic molecules.** / Gajdos, Fruzsina; Valner, Siim; Hoffmann, Felix; Spencer, Jacob; Breuer, Marian; Kubas, Adam; Dupuis, Michel; Blumberger, Jochen.

Research output: Contribution to journal › Article

*Journal of Chemical Theory and Computation*, vol. 10, no. 10, pp. 4653-4660. https://doi.org/10.1021/ct500527v

}

TY - JOUR

T1 - Ultrafast estimation of electronic couplings for electron transfer between pi;-conjugated organic molecules

AU - Gajdos, Fruzsina

AU - Valner, Siim

AU - Hoffmann, Felix

AU - Spencer, Jacob

AU - Breuer, Marian

AU - Kubas, Adam

AU - Dupuis, Michel

AU - Blumberger, Jochen

PY - 2014/10/14

Y1 - 2014/10/14

N2 - Simulation of charge transport in organic semiconducting materials requires the development of strategies for very fast yet accurate estimation of electronic coupling matrix elements for electron transfer between organic molecules (transfer integrals, Hab). A well-known relation that is often exploited for this purpose is the approximately linear dependence of electronic coupling with respect to the overlap of the corresponding diabatic state wave functions for a given donor-acceptor pair. Here we show that a single such relation can be established for a large number of different pi;-conjugated organic molecules. In our computational scheme the overlap of the diabatic state wave function is simply estimated by the overlap of the highest singly occupied molecular orbital of donor and acceptor, projected on a minimum valence shell Slater-type orbital (STO) basis with optimized Slater decay coefficients. After calibration of the linear relation, the average error in Hab as obtained from the STO orbital overlap is a factor of 1.9 with respect to wave function-theory validated DFT calculations for a diverse set of pi;-conjugated organic dimers including small arenes, arenes with S, N, and O heteroatoms, acenes, porphins, and buckyballs. The crucial advantage of the scheme is that the STO orbital overlap calculation is analytic. This leads to speedups of 6 orders of magnitude with respect to reference DFT calculations, with little loss of accuracy in the regime relevant to charge transport in organics.

AB - Simulation of charge transport in organic semiconducting materials requires the development of strategies for very fast yet accurate estimation of electronic coupling matrix elements for electron transfer between organic molecules (transfer integrals, Hab). A well-known relation that is often exploited for this purpose is the approximately linear dependence of electronic coupling with respect to the overlap of the corresponding diabatic state wave functions for a given donor-acceptor pair. Here we show that a single such relation can be established for a large number of different pi;-conjugated organic molecules. In our computational scheme the overlap of the diabatic state wave function is simply estimated by the overlap of the highest singly occupied molecular orbital of donor and acceptor, projected on a minimum valence shell Slater-type orbital (STO) basis with optimized Slater decay coefficients. After calibration of the linear relation, the average error in Hab as obtained from the STO orbital overlap is a factor of 1.9 with respect to wave function-theory validated DFT calculations for a diverse set of pi;-conjugated organic dimers including small arenes, arenes with S, N, and O heteroatoms, acenes, porphins, and buckyballs. The crucial advantage of the scheme is that the STO orbital overlap calculation is analytic. This leads to speedups of 6 orders of magnitude with respect to reference DFT calculations, with little loss of accuracy in the regime relevant to charge transport in organics.

UR - http://www.scopus.com/inward/record.url?scp=84907970157&partnerID=8YFLogxK

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U2 - 10.1021/ct500527v

DO - 10.1021/ct500527v

M3 - Article

VL - 10

SP - 4653

EP - 4660

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 10

ER -