Theoretical Study of Long-Distance Electronic Coupling in H2C(CH2)n-2 CH2 Chains, n=3-16

Curtiss, Larry A.; Naleway, Conrad A.; Miller, John R.

doi:10.1021/j100118a600

Cited by 88 publications

(96 citation statements)

References 2 publications

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“…[21][22][23] Consequently, the Koopmans' thereom transfer integral for hole transfer calculated using the 3-21G basis set may be too small. This was checked using the procedure of the ghost atom method of Curtiss et al 23 for DN-4S, where such effects should be most apparent.…”

Section: Resultsmentioning

confidence: 99%

Through-Bond and Through-Space Coupling in Photoinduced Electron and Energy Transfer: An ab Initio and Semiempirical Study

et al. 1996

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Ab initio and semiempirical calculations of transfer integrals for electron transfer and energy transfer have been carried out on rigidly linked norbornane-bridged naphthalene dimers to gain insight into the relative importance of through-bond and through-space interactions on photoinduced energy and electron transfer processes. In the absence of direct through-space orbital overlap between the naphthalene moieties, throughbond interaction involving the linking polynorbornane bridge is found to significantly enhance the transfer integrals for electron transfer and triplet-triplet energy transfer. For singlet-singlet energy transfer direct through-space Coulombic interaction between the naphthalene moieties is non-negligible at the separations considered and acts to reinforce the through-bond interaction. The relationship between electron and energy transfer processes and the application of these results to the interpretation of recent experimental data are discussed.

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Section: Resultsmentioning

confidence: 99%

Through-Bond and Through-Space Coupling in Photoinduced Electron and Energy Transfer: An ab Initio and Semiempirical Study

et al. 1996

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“…Various schemes have been proposed in the literature [4,5,23,24] for a proper choice of the one-electron orbital energies in Eq. (10).…”

Section: Theory and Calculationsmentioning

confidence: 99%

“…The coupling element, V DA , can be calculated either for the cation or anion from the respective ionization potential (IP) and electron affinity (EA) energy levels within the KT approximation. The detailed theoretical analysis of various approaches can be found elsewhere [4,5,23,24]. Here, we have used the highest occupied (HO) and next-highest occupied (NHO)) molecular orbitals of the neutral triplet (M S ϭ 3) diradical to calculate V DA as [24],…”

Section: Theory and Calculationsmentioning

confidence: 99%

“…The simplicity and relatively less computational demands associated with the KT approach have made it an attractive choice for investigating ET properties of complex organic and biological systems [3,4-6,9,20,24 -26]. Previous studies have shown [7,[23][24][25][26] that the accuracy of the V DA calculated by KT approach is comparable to those obtained from more rigorous techniques, such as the Marcus-Hush (MH) twostate model [21,22]. In order to further assess the accuracy of V DA for linear -electron chain molecules obtained with the use of the KT approach, we calculated the coupling matrix element for 1,3-trans-butadiene using Eq.…”

Section: Theory and Calculationsmentioning

confidence: 99%

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Length‐dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study

Mallick

Karna

et al. 2009

Int J of Quantum Chemistry

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ABSTRACT:The electron transfer (ET) properties of -electron conjugated quasione-dimensional molecular wires, consisting of polyene, [ϾCACϽ] n (n ϭ 1-11), including ␤-carotene, is investigated using ab initio molecular orbital theory within Koopmans theorem (KT) approach. The ET coupling matrix element, V DA , for 1,3-transbutadiene molecule calculated with the KT approach shows excellent agreement with the corresponding results obtained with two-state model. The calculated values of V DA for the polyene oligomers exhibit exponential decrease in magnitude with increasing length of the wire. However, the decay curve exhibits three different regimes. The magnitude of the decay constant, ␤, decreases with the increase in length of the wire. A highly delocalized -electron cloud in the polyene chain appears to facilitate retention of the electronic coupling at large separations between the donor and acceptor centers.

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“…Given that the systems examined below are not in closecontact ͑i.e., weakly interacting͒ the description of the longrange behavior of the wave functions is important in obtaining converged electronic coupling elements. This is to be distinguished from the basis set dependence of H ab for longrange et in covalently bonded systems, 49 where it has been shown that modest basis sets can yield converged results, due to the relatively large overlap of atomic orbitals on adjacent atoms. For weakly interacting systems one possible concern would be that basis set superposition errors ͑BSSE͒ 50 ͑due to basis set incompleteness͒ might have a significant effect on the value of H ab .…”

Section: B One-electron Basis Setsmentioning

confidence: 99%

An ab initio study of specific solvent effects on the electronic coupling element in electron transfer reactions

Henderson¹,

Cave²

1998

The Journal of Chemical Physics

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Specific solvent effects on the electronic coupling element for electron transfer are examined using two model donor-acceptor systems (Zn 2 ϩ and Li 2 ϩ ) and several model ''solvent'' species (He, Ne, H 2 O, and NH 3 ). The effects are evaluated relative to the given donor-acceptor pair without solvent present. The electronic coupling element (H ab ) is found to depend strongly on the identity of the intervening solvent, with He atoms decreasing H ab , whereas H 2 O and NH 3 significantly increase H ab . The distance dependence ͑essentially exponential decay͒ is weakly affected by a single intervening solvent atom-molecule. However, when the donor-acceptor distance increases in concert with addition of successively greater numbers of solvent species, the decay with distance of H ab is altered appreciably. Effects due to varying the orientation of molecular solvent are found, somewhat surprisingly, to be quite modest.

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Theoretical Study of Long-Distance Electronic Coupling in H₂C(CH₂)_n-2 CH₂ Chains, n=3-16

Cited by 88 publications

References 2 publications

Through-Bond and Through-Space Coupling in Photoinduced Electron and Energy Transfer: An ab Initio and Semiempirical Study

Through-Bond and Through-Space Coupling in Photoinduced Electron and Energy Transfer: An ab Initio and Semiempirical Study

Length‐dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study

An ab initio study of specific solvent effects on the electronic coupling element in electron transfer reactions

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