Electric-field induced intramolecular electron transfer in spiro .pi.-electron systems and their suitability as molecular electronic devices. A theoretical study

Farazdel, Abbas; Dupuis, Michel; Clementi, E.; Aviram, Ari

doi:10.1021/ja00167a016

Cited by 360 publications

(372 citation statements)

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“…The latter algorithms require the use of some auxiliary basis sets, which are however always taken from the corresponding hardwired library. 43 Complementarily, the electronic coupling was calculated by the electron transfer module of NWChem 6.3, 44 which utilises the method of Corresponding Orbital Transformation 45 to calculate rigorously the coupling from the wavefunctions of the reactant and product states. [46][47][48] …”

Section: B Computational Detailsmentioning

confidence: 99%

Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

Sancho‐García

Pérez-Jiménez

2014

The Journal of Chemical Physics

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We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π -stacks with dimer stabilization energies ranging from -20 to -30 kcal mol −1 at close distances around 3.0-3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings).

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Section: B Computational Detailsmentioning

confidence: 99%

Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

Sancho‐García

Pérez-Jiménez

2014

The Journal of Chemical Physics

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“…For the general case, including intramolecular processes, one can employ the symmetry-broken (SB) SCF method, applicable when distinct charge-localized (and generally non-orthogonal) initial and final SB SCF states can be obtained. 13,15,[51][52][53][54] The nonperturbative GMH model 31,46 (an extension of the Mulliken Hush…”

Section: The Generalized Mulliken Hush (Gmh) Modelmentioning

confidence: 99%

Reduced Electronic Spaces for Modeling Donor/Acceptor Interactions

et al. 2010

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Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (H DA ) and effective D/A separation distances (r DA ), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin-Day class III and as well as class II situations. Once the electronic state space is selected (a set of n g 2 adiabatic states approximated by an orbital space based on an effective 1-electron (1-e) Hamiltonian), the charge-localized GMH diabatic states are obtained as the eigenstates of the dipole moment operator, with rotations to yield locally adiabatic states for sites with multiple states. The 1-e states and energies are expressed in terms of Kohn-Sham orbitals and orbital energies. Addressing questions as to whether the estimate of H DA "improves" as one increases n, and in what sense the GMH approach "converges" with n, we carry out calculations for three mixed-valence binuclear Ru complexes, from which we conclude that the 2-state (2-st) model gives the most appropriate estimate of the effectiVe coupling, similar (to within a rms deviation of e15%) to coupling elements obtained by superexchange correction of H DA values based on larger spaces (n ) 3-6), and thus yielding a quasi-invariant value for H DA over the range explored in the calculations (n ) 2-6). An analysis of the coupling and associated D and A states shows that the 2-st coupling involves crucial mixing with intervening bridge states (D and A "tails"), while increasingly larger state spaces for the same system yield increasingly more localized D and A states (and weaker coupling), with H DA tending to approach the limit of "bare" or "through space" coupling. These results help to reconcile seemingly contradictory assertions in the recent literature regarding the proper role of multistate frameworks in the formulation of coupling for both intra-and intermolecular ET systems.The present results are compared in detail with other reported results.

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“…These carborane molecules will be referred to in the rest of this Letter as 10-vertex and 12-vertex carborane molecules, respectively. The ET coupling strength is calculated using the MH two-state model [17][18][19][20][21] within ab initio Hartree-Fock theory. The effects of basis sets and geometrical parameters on the ET coupling strength are also investigated.…”

Section: Introductionmentioning

confidence: 99%