Multistate Effects in Calculations of the Electronic Coupling Element for Electron Transfer Using the Generalized Mulliken−Hush Method

Rust, M; Lappe, Jason; Cave, Robert J.

doi:10.1021/jp0142886

Cited by 98 publications

(106 citation statements)

References 44 publications

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“…The donoracceptor couplings calculated using the two-and three-state schemes are 1.72 and 2.46 meV, respectively. If donor and acceptor are almost in resonance ͑F = 6.725ϫ 10 −5 a.u.͒, the difference 2 − 1 = 0.29 D is remarkably smaller than 13 = 0.71 D. However, the two-and three-state couplings are similar ͑1.63 and 2.37 meV͒ to the estimates found at F =0. Furthermore, according to our experience, in nonsymmetric systems the difference 2 − 1 is often essentially larger than transition moments; however, the performance of the twostate model strongly depends on the system being considered.…”

Section: Effects Of External Parameters On Adiabatic and Diabatic Promentioning

confidence: 63%

“…Electron transition 1 → 2 results in a considerable change of the adiabatic dipole moment 2 − 1 Ϸ 31.8 D. Because the state 3 is mainly localized on the bridge, 3 − 1 = 2 − 3 =1/2͑ 2 − 1 ͒. The transition moment 12 of ϳ2.7 D is essentially larger than 13 and 23 . The d-a electronic coupling V da is by order of magnitude smaller than the matrix elements V db and V ab associated with the bridge state.…”

Section: Effects Of External Parameters On Adiabatic and Diabatic Promentioning

confidence: 97%

“…Rust et al considered where two diabatic states ͑the ground state and a locally excited state͒ are localized on the donor and a single-electron transfer state is localized on the acceptor. 13 They developed a diagnostic for determining when a third state has to be considered within GMH calculations. Recently, a multistate GMH approach has been employed for calculating electronic couplings for charge transfer in DNA stacks consisting of three, four, and five base pairs.…”

Section: ͑1͒mentioning

confidence: 99%

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Estimation of electronic coupling in π-stacked donor-bridge-acceptor systems: Correction of the two-state model

Voityuk

2006

The Journal of Chemical Physics

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Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of V da because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a stack, where donor and acceptor are separated by a bridging unit, can be obtained, where E 1 , E 2 , and E 3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, ij is the transition dipole moments between the states i and j, and R da is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement ͑within 5%͒ with the data of the three-state generalized Mulliken-Hush model.

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Section: Effects Of External Parameters On Adiabatic and Diabatic Promentioning

confidence: 63%

Section: Effects Of External Parameters On Adiabatic and Diabatic Promentioning

confidence: 97%

Section: ͑1͒mentioning

confidence: 99%

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Estimation of electronic coupling in π-stacked donor-bridge-acceptor systems: Correction of the two-state model

Voityuk

2006

The Journal of Chemical Physics

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“…Diabatization approximations are particularly suited for evaluating excitonic couplings between several excited states. [26][27][28][29] Recently, some of us have developed a diabatization scheme to compute excitonic couplings between molecular crystal pairs beyond the two-level approximation. 30 The great advantage of diabatization schemes is that they can deal with the short-range (exchange and overlap) and long-range (Coulombic) contributions of the excitonic couplings on equal footing.…”

Section: Introductionmentioning

confidence: 99%

Exciton Dynamics in Phthalocyanine Molecular Crystals

2016

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In this paper, the exciton transport properties of an octa(butyl)-substituted metal-free phthalocyanine (H2-OBPc) molecular crystal have been explored by means of a combined computational (molecular dynamics and electronic structure calculations) and theoretical (model Hamiltonian) approximation. The excitonic couplings in phthalocyanines, where multiple quasi-degenerate excited states are present in the isolated chromophore, are computed with a multistate diabatization scheme which is able to capture both short-and long-range excitonic coupling effects. Thermal motions in phthalocyanine molecular crystals at room temperature cause substantial fluctuation of the excitonic couplings between neighboring molecules (dynamic disorder). The average values of the excitonic couplings are found to be not much smaller than the reorganization energy for the excitation energy transfer and the commonly assumed incoherent regime for this class of materials cannot be invoked. A simple but realistic model Hamiltonian is proposed to study the exciton dynamics in phthalocyanine molecular crystals or aggregates beyond the incoherent regime.2

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“…24,25 For , which may involve exciplex formation) 27 )susing the appropriate 2-st models in a pairwise fashion. However, if the states interact strongly with each other, a 3-state treatment may be required, especially in the case of radiative CR, which may involve significant intensity borrowing or other types of vibronic coupling.…”

Section: Introductionmentioning

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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Multistate Effects in Calculations of the Electronic Coupling Element for Electron Transfer Using the Generalized Mulliken−Hush Method

Cited by 98 publications

References 44 publications

Estimation of electronic coupling in π-stacked donor-bridge-acceptor systems: Correction of the two-state model

Estimation of electronic coupling in π-stacked donor-bridge-acceptor systems: Correction of the two-state model

Exciton Dynamics in Phthalocyanine Molecular Crystals

Reduced Electronic Spaces for Modeling Donor/Acceptor Interactions

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