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Reorganization Energy (reorganization + energy)

Distribution by Scientific Domains
Chemistry75%

Kinds of Reorganization Energy

  • solvent reorganization energy
    		•

    Selected Abstracts

    Modeling Electron and Hole Transport in Fluoroarene-Oligothiopene Semiconductors: Investigation of Geometric and Electronic Structure Properties,

    ADVANCED FUNCTIONAL MATERIALS, Issue 2 2008
    E. Koh
    Abstract A theoretical study using density functional theory is undertaken to gain insight into how the structural, electronic, and electron-transfer characteristics of three Fluoroarene-oligothiophene semiconductors influence the preferred transport of electrons versus holes in field-effect transistor applications. The intermolecular electronic coupling interactions are analyzed through both a simplified energy-splitting in dimer (ESID) model and as a function of the entire dimer Hamiltonian in order to understand the impact of site energy differences; our results indicate that these differences are generally negligible for the series and, hence, use of the ESID model is valid. In addition, we also investigate the reduction and oxidation processes to understand the magnitudes of the intramolecular reorganization energy for the charge-hopping process and expected barrier heights for electron and hole injection into these materials. From the electronic coupling and intramolecular reorganization energies, estimates of the nearest-neighbor electron-transfer hopping rate constant for electrons are obtained. The ionization energetics suggest favored electron injection for the system with perfluoroarene groups at the end of the thiophene core, in agreement with experiments. The combined analyses of the electron-transfer properties and ionization processes suggest possible ambipolar behavior for these materials under favorable device conditions. [source]

    Charge transport in stacking metal and metal-free phthalocyanine iodides.

    JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2009
    Effects of packing, central metals, core modification, dopants, external electric field, substitutions
    Abstract The charge-transport properties of the one-dimensional stacking metal phthalocyanine iodides (M(Pc)I, M = Fe, Co, Ni, Cu) and metal-free phthalocyanine iodide (H2(Pc)I) have been theoretically investigated. On the basis of the tight-binding approximation and two-state theory, both the site-energy corrected energy splitting in dimer and Fock-matrix-based methods are used to calculate the transfer integral. The intermolecular motions, including interplanar translation, rotation, slip, and tilt, exert remarkable impacts on the transfer integral. The order/disorder of the dopant stack and the long-range electrostatic interactions are also demonstrated to be crucial factors for modulation of charge-transport properties. The transfer integral undergoes slight changes under an applied electric field along the stacking direction in the range of 106 , 107 V cm,1. The change of central metals in MPc has little effect on the transfer integrals, but significantly affects the reorganization energies. The extension of the ,-conjugation in macrocyclic ligand brings about considerable influence on the transfer integrals. Peripheral substitutions by animo, hydroxyl, and methyl lead to deviations from planarity of macromolecular rings, and hence affect the valence bands significantly. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 [source]

    Tris(4-bromophenyl)aminium hexachloridoantimonate (`Magic Blue'): a strong oxidant with low inner-sphere reorganization

    ACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2010
    Mauricio Quiroz-Guzman
    Both the radical cation tris(4-bromophenyl)aminium hexachloridoantimonate (`Magic Blue'), (C18H12Br3N)[SbCl6], (I), and neutral tris(4-bromophenyl)amine, C18H12Br3N, (II), show extremely similar three-bladed propeller structures with planar N atoms. Key geometric features, such as the C,N bond distances and the angles between the planes of the aryl groups and the central NC3 plane, are identical within experimental uncertainty in the two structures. This contrasts with the significant structural changes observed on oxidation of more electron-rich triarylamines, where resonance contributes to the stabilization of the radical cation, and suggests that, in general, more strongly oxidizing triarylaminium cations will have lower inner-sphere reorganization energies than their lower-potential analogues. [source]

    Modeling Electron and Hole Transport in Fluoroarene-Oligothiopene Semiconductors: Investigation of Geometric and Electronic Structure Properties,

    ADVANCED FUNCTIONAL MATERIALS, Issue 2 2008
    E. Koh
    Abstract A theoretical study using density functional theory is undertaken to gain insight into how the structural, electronic, and electron-transfer characteristics of three Fluoroarene-oligothiophene semiconductors influence the preferred transport of electrons versus holes in field-effect transistor applications. The intermolecular electronic coupling interactions are analyzed through both a simplified energy-splitting in dimer (ESID) model and as a function of the entire dimer Hamiltonian in order to understand the impact of site energy differences; our results indicate that these differences are generally negligible for the series and, hence, use of the ESID model is valid. In addition, we also investigate the reduction and oxidation processes to understand the magnitudes of the intramolecular reorganization energy for the charge-hopping process and expected barrier heights for electron and hole injection into these materials. From the electronic coupling and intramolecular reorganization energies, estimates of the nearest-neighbor electron-transfer hopping rate constant for electrons are obtained. The ionization energetics suggest favored electron injection for the system with perfluoroarene groups at the end of the thiophene core, in agreement with experiments. The combined analyses of the electron-transfer properties and ionization processes suggest possible ambipolar behavior for these materials under favorable device conditions. [source]

    Nonequilibrium solvent polarization in kinetics of SN2 reactions

    INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2003
    J. S. JaworskiArticle first published online: 21 NOV 200
    The solvent effect on the experimental activation barriers for the reactions of methyl iodide with chloride and thiocyanate ions was analyzed according to the Marcus and Shaik theories, considering SN2 mechanism in terms of a single electron shift. The linear increase in the solvent reorganization energy of the Marcus theory (after removing contributions from the specific solvation) with the solvent Pekar factor, describing the effect of the nonequilibrium solvent polarization, was observed for six aprotic solvents. The direct support of the title effect based on the Shaik theory was less evident; however, in general, the calculated activation barriers in 10 solvents change parallel with the experimental ones. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 61,66, 2003 [source]

    Theoretical study on the influence of ancillary ligand on the spectroscopic properties and electronic structures of phosphorescent Pt(II) complexes

    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2010
    Min Zhang
    Abstract The geometries, energies, and electronic properties of a series of phosphorescent Pt(II) complexes including FPt, CFPt, COFPt, and NFPt have been characterized within density functional theory DFT calculations which can reproduce and rationalize experimental results. The properties of excited-states of the Pt(II) complexes were characterized by configuration interaction with singles (CIS) method. The ground- and excited-state geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. In addition, we also have performed a triplet UB3LYP optimization for complex FPt and compared it with CIS method in the emission properties. The datum (562.52 nm) of emission wavelength for complex FPt, which were computed based on the triplet UB3LYP optimization excited-state geometry, is not agreement with the experiment value (500 nm). The absorption and phosphorescence wavelengths were computed based on the optimized ground- and excited-state geometries, respectively, by the time-dependent density functional theory (TD-DFT) methods. The results revealed that the nature of the substituent at the phenylpyridine ligand can influence the distributions of HOMO and LUMO and their energies. Moreover, the auxiliary ligand pyridyltetrazole can make the molecular structure present a solid geometry. In addition, the charge transport quality has been estimated approximately by the predicted reorganization energy (,). Our result also indicates that the substitute groups and different auxiliary ligand not only change the nature of transition but also affect the rate and balance of charge transfer. By summarizing the results, we can conclude that the NFPt is good OLED materials with a solid geometry and a balanced charge transfer rate. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source]

    Theoretical study on the spectroscopic properties and electronic structures of heteroleptic phosphorescent Ir(III) complexes

    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2009
    Min Zhang
    Abstract The geometries, spectroscopic and electronic structures properties of a series of heteroleptic phosphorescent Ir(III) complexes including N981, N982, N983, N984 have been characterized by density functional theory calculations. The excited-state properties of the Ir(III) complexes have been characterized by CIS method. The ground- and excited-state geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. By using the time-dependent density functional theory method, the absorption and phosphorescence spectra were calculated based on the optimized ground- and excited-state geometries, respectively. The results show that the absorption and emission data agree well with the corresponding experimental results. The calculated results also revealed that the nature of the substituent at the 4-position of the pyridyl moiety can influence the distributions of HOMO and LUMO and their energies. In addition, the charge transport quality has been estimated approximately by the calculated reorganization energy (,). Our result also indicates that the positions of the substitute groups not only change the transition characters but also affect the charge transfer rate and balance, and complex N982 is a very good charge transfer material for green OLEDs. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source]

    Comparison of basis set effects and the performance of ab initio and DFT methods for probing equilibrium fluctuations

    JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2007
    Ross C. Walker
    Abstract The electronic absorption and emission spectra of large molecules reflect the extent and timescale of electron-vibration coupling and therefore the extent and timescale of relaxation/reorganization in response to a perturbation. In this paper, we present a comparison of the calculated absorption and emission spectra of NADH in liver alcohol dehydrogenase (LADH), using quantum mechanical/molecular mechanical methods, in which we vary the QM component. Specifically, we have looked at the influence of basis set (STO-3G, 3-21G*, 6-31G*, CC-pVDZ, and 6-311G**), as well as the influence of applying the DFT TD-B3LYP and ab initio TD-HF and CIS methods to the calculation of absorption/emission spectra and the reorganization energy (Stokes shift). The ab initio TD-HF and CIS methods reproduce the experimentally determined Stokes shift and spectral profiles to a high level of agreement, while the TD-B3LYP method significantly underestimates the Stokes shift, by 45%. We comment on the origin of this problem and suggest that ab initio methods may be naturally more suited to predicting molecular behavior away from equilibrium geometries. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 478,490, 2007 [source]

    Looking for a contribution of the non-equilibrium solvent polarization to the activation barrier of the SN2 reaction

    JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6 2002
    Jan S. Jaworski
    Abstract The solvent effect on the activation free energy of the Finkelstein reaction between methyl iodide and Cl, ions was analysed in terms of the recent Marcus theory unifying the SN2 and the electron transfer reactions. The homolytic bond dissociation energy and the related resonance energy of interaction of the states seem to be almost solvent independent. The sum of the work term wr and the solvent reorganization energy ,0/4 depends strongly on the solvent acidity parameter, e.g. ETN, describing the solvation/desolvation of anions. However, after removing the contribution of the specific solvation the linear increase of the remaining part of ,0/4 with the Pekar factor, describing the non-equilibrium solvent polarization, was observed for six aprotic solvents. Copyright © 2002 John Wiley & Sons, Ltd. [source]

    Excited Singlet (S1)-state Interactions of Nile Red with Aromatic Amines,

    PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2003
    J. Mohanty
    ABSTRACT Both steady-state (SS) and time-resolved (TR) studies show that the fluorescence of the dye Nile red (NR) is quenched by various aromatic amines (ArA). Bimolecular quenching constants (kq) from both SS and TR measurements are observed to match well, indicating that the interaction is dynamic in nature. The quenching interaction in the present systems has been attributed to electron transfer (ET) from ArA to excited NR, based on the variations in the kq values with the oxidation potentials of the amines. The kq values calculated within the framework of Marcus' outer-sphere ET theory at different free-energy changes (,G0) of the ET reactions match well with the experimental ones, supporting the ET mechanism in the systems studied. The reorganization energy (,) estimated from the correlation of the experimental and the calculated kq values is quite similar to the solvent reorganization energy (,s), calculated on the basis of the solvent dielectric continuum model along with the assumption that the reactants are the effective spheres. Although a modest error is involved in this ,s calculation, the similarity in , and ,s values suggests that the solvent reorganization plays a dominant role in governing the ET dynamics in the present systems. [source]

    Conductance through a redox system in the Coulomb blockade regime: Many-particle effects and influence of electronic correlations

    PHYSICA STATUS SOLIDI - RAPID RESEARCH LETTERS, Issue 1-2 2010
    Sabine Tornow
    Abstract We investigate the transport characteristics of a redox system weakly coupled to leads in the Coulomb blockade regime. The redox system comprises a donor and acceptor separated by an insulating bridge in a solution. It is modeled by a two-site extended Hubbard model which includes on-site and inter-site Coulomb interactions and the coupling to a bosonic bath. The current,voltage characteristics is calculated at high temperatures using a rate equation approach. For high voltages exceeding the Coulomb repulsion at the donor site the calculated transport characteristics exhibit pronounced deviations from the behavior expected from single-electron transport. Depending on the relative sizes of the effective on-site and inter-site Coulomb interactions on one side and the reorganization energy on the other side we find either negative differential resistance or current enhancement. Schematic view of the redox system with donor (D) and acceptor (A) coupled to the leads L and R. The electronic degrees of freedom of the DA system are coupled to the environment comprising internal vibrations and the solvent dynamics. The current is calculated as a function of the bias voltage Vb and gate voltage Vg. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

    Fast structural dynamics in reduced and oxidized cytochrome c

    PROTEIN SCIENCE, Issue 3 2009
    Weixia Liu
    Abstract The sub-nanosecond structural dynamics of reduced and oxidized cytochrome c were characterized. Dynamic properties of the protein backbone measured by amide 15N relaxation and side chains measured by the deuterium relaxation of methyl groups change little upon change in the redox state. These results imply that the solvent reorganization energy associated with electron transfer is small, consistent with previous theoretical analyses. The relative rigidity of both redox states also implies that dynamic relief of destructive electron transfer pathway interference is not operational in free cytochrome c. [source]

    Efficient Charge Injection from the S2 Photoexcited State of Special-Pair Mimic Porphyrin Assemblies Anchored on a Titanium-Modified ITO Anode

    CHEMISTRY - A EUROPEAN JOURNAL, Issue 31 2006
    Mitsuhiko Morisue Dr.
    Abstract A novel surface fabrication methodology has been accomplished, aimed at efficient anodic photocurrent generation by a photoexcited porphyrin on an ITO (indium,tin oxide) electrode. The ITO electrode was submitted to a surface sol,gel process with titanium n -butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium-treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped-cofacial porphyrin dimers, the so-called artificial special pair at the photoreaction center, were organized through imidazolyl-to-zinc complementary coordination of imidazolylporphyrinatozinc(II) units, which were covalently immobilized by ring-closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X-ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat-band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15,%, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S2 level into the conduction band of the ITO electrode takes place before internal conversion to the S1* state, through the strong electronic communication of the phosphonyl anchor with the sol,gel-modified ITO surface. [source]

    Photoinduced Electron Transfer in ,-Cyclodextrin-Based Supramolecular Dyads: A Free-Energy-Dependence Study

    CHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2006
    Bijitha Balan
    Abstract Photoinduced electron transfer (PET) between ,-cyclodextrin-appended pyrene (PYCD) and a few acceptor molecules was studied in aqueous solutions. The pyrene moiety in PYCD is located above the narrower rim of the ,-CD and is fully exposed to water. The acceptors are monocyclic organic molecules and, upon dissolution in water in the presence of PYCD, a fraction of the donor,acceptor systems is present as supramolecular dyads and the remaining fraction as free molecules. Free-energy-dependence studies showed that electron transfer in the supramolecular dyads follows the Marcus equation. The donor,acceptor coupling and the reorganization energy were determined from fits of the data to the Marcus equation. The electronic coupling was found to be similar to those reported for hydrogen-bonded systems. It appears that the actual ,out values are somewhat lower than values calculated with the continuum model. The experimental design has also allowed, for the first time, a visual demonstration of the inverted region on the basis of the raw fluorescence lifetime data. [source]

    Photoinduced Electron Transfer Reactions by SmI2 in THF: Luminescence Quenching Studies and Mechanistic Investigations

    CHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2005
    Edamana Prasad Dr.
    Abstract Photoluminescence quenching studies of SmI2 in dry THF were carried out in the presence of five different classes of compounds: ketone, alkyl chloride, nitrile, alkene and imine. The free energy change (,G,0) of the photoinduced electron transfer (PET) reactions was calculated from the redox potentials of the donor (SmI2) and acceptors. The bimolecular quenching constants (kq) derived from the Stern,Volmer experiments parallel the free energy changes of the PET processes. The observed quenching constants were compared with the theoretically derived electron transfer rate constants (ket) from Marcus theory and found to be in good agreement when a value of ,=167 kJ,mol,1 (40 kcal,mol,1) was used for the reorganization energy of the system. A careful comparison of the excited state dynamics of SmII in the solid state to the results obtained in solution (THF) provides new insight in to the excited states of SmII in THF. The activation parameters determined for the PET reactions in SmI2/1-chlorobutane system are consistent with a less ordered transition state and high degree of bond reorganization in the activated complex compared to similar ground state reactions. Irradiation studies clearly show that SmI2 acts as a better reductant in the excited state and provides an alternative pathway for rate enhancement in known and novel functional group reductions. [source]

    The Origin of the Improved Efficiency and Stability of Triphenylamine-Substituted Anthracene Derivatives for OLEDs: A Theoretical Investigation,

    CHEMPHYSCHEM, Issue 17 2008
    Bing Yang Dr.
    Abstract Herein, we describe the molecular electronic structure, optical, and charge-transport properties of anthracene derivatives computationally using density functional theory to understand the factors responsible for the improved efficiency and stability of organic light-emitting diodes (OLEDs) with triphenylamine (TPA)-substituted anthracene derivatives. The high performance of OLEDs with TPA-substituted anthracene is revealed to derive from three original features in comparison with aryl-substituted anthracene derivatives: 1) the HOMO and LUMO are localized separately on TPA and anthracene moieties, respectively, which leads to better stability of the OLEDs due to the more stable cation of TPA under a hole majority-carrier environment; 2) the more balanceable hole and electron transport together with the easier hole injection leads to a larger rate of hole,electron recombination, which corresponds to the higher electroluminescence efficiency; and 3) the increasing reorganization energy for both hole and electron transport and the higher HOMO energy level provide a stable potential well for hole trapping, and then trapped holes induce a built-in electric field to prompt the balance of charge-carrier injection. [source]