A modified two-sphere model for solvent reorganization energy in electron transfer

Wu, Han Yu; Ren, Hai Sheng; Zhu, Quan; Li, Xiang Yuan

doi:10.1039/c2cp23759h

Cited by 21 publications

(13 citation statements)

References 38 publications

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“…When we consider a nonequilibrium polarization, the solvent reorganization energy is defined 33 and regarded as the cost of maintaining the residual polarization P 0 . In our previous work, we proved by means of the constraining equilibrium principle that the solvent reorganization energy is exactly the negative value of the equilibrium solvation energy due to P 0 in the medium of e s , i.e.…”

Section: Thermodynamics Of Constrained Equilibrium and The Expression...mentioning

confidence: 99%

“…7,8,27,29 Recently, we proposed a new formula for the electrostatic solvation energy of nonequilibrium polarization by introducing the constrained equilibrium approach in the continuum model. 30,31 This formula has been successfully applied to evaluate the reorganization energy of electron transfer reactions, 32,33 vertical ionization energy of hydrated electrons. 34 In the present work, we propose a new analytical model for the absorption spectral shift.…”

Section: Introductionmentioning

confidence: 99%

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Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy

Ren

Zhu

et al. 2012

Phys. Chem. Chem. Phys.

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According to our recent studies on the nonequilibrium solvation, the solvent reorganization energy is found to be the cost of maintaining the residual polarization P', which equilibrates with the extra electric field E(ex). On the basis of this solvent reorganization energy and the well-established equilibrium solvation energy, a novel and reasonable expression for the spectral shift of the electronic absorption spectra is proposed in this work. Furthermore, the two lowest transitions of uracil in aqueous solution are investigated as test cases with the TDDFT/6-311++G** method. The obtained spectral shift is 0.48 eV for n → π* transition and -0.14 eV for π → π* transition, agreeing well with available experimental results. The contributions to the shift are discussed and the electrostatic plus polarization components are found to be crucial for the electronic absorption spectra of uracil in aqueous solution.

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Section: Thermodynamics Of Constrained Equilibrium and The Expression...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy

Ren

Zhu

et al. 2012

Phys. Chem. Chem. Phys.

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“…The same is true for the amended Marcus formula for λ s (Eq. ):

true λ_{s} = \frac{e^{2}}{8 π ϵ_{0}} (\frac{1}{R_{A}} + \frac{1}{R_{D}} - \frac{2}{R_{A D}}) {(\frac{1}{n^{2}} - \frac{1}{ϵ})}^{2} \frac{1}{1 - ϵ^{- 1}}

…”

Section: Resultsmentioning

confidence: 99%

Highly Polarized Coumarin Derivatives Revisited: Solvent‐Controlled Competition Between Proton‐Coupled Electron Transfer and Twisted Intramolecular Charge Transfer

Morawski

Kielesiński

Gryko

et al. 2020

Chemistry A European J

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Linking a polarized coumarin unit with an aromatic substituent via an amide bridge results in weak electronic coupling that affects the intramolecular electron‐transfer (ET) process. As a result of this, interesting solvent‐dependent photophysical properties can be observed. In polar solvents, electron transfer in coumarin derivatives of this type induces a mutual twist of the electron‐donating and ‐accepting molecular units (TICT process) that facilitates radiationless decay processes (internal conversion). In the dyad with the strongest intramolecular hydrogen bond, the planar form is stabilized, such that twisting can only occur in highly polar solvents, whereas a fast proton‐coupled electron‐transfer (PCET process) occurs in nonpolar n‐alkanes. The kPCET rate constant decreases linearly with the energy of the fluorescence maximum in different solvents. This observation can be explained in terms of competition between electron‐ and proton‐transfer from a highly polarized (ca. 15 D) and fluorescent locally excited (1LE) state to a much less polarized (ca. 4 D) charge‐transfer (1CT) state, a unique occurrence. Photophysical measurements performed for a family of related coumarin dyads, together with results of quantum‐chemical computations, give insight into the mechanism of the ET process, which is followed by either a TICT or a PCET process. Our results reveal that dielectric solvation of the excited state slows down the PCET process, even in nonpolar solvents.

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“…Many authors, however, have empirically considered the value of λ s in the range of 0.2 to 1.0 eV for different organic molecules. () In our study, we have taken λ s to be 0.4 eV. Nevertheless, it is worthy of mention that, the external reorganization energy has noticeable influence on the mobility of the organic compounds, which is discussed in the next section.…”

Section: Resultsmentioning

confidence: 99%

Charge transport and prototypical optical absorptions in functionalized zinc phthalocyanine compounds: A density functional study

Sahoo

Sahu

Sharma

2017

J of Physical Organic Chem

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Metal phthalocyanines are considered to be prominent candidates for designing organic semiconductors. However, enhancing n‐type characteristics and air stability in these compounds have been the major challenges. Earlier studies on zinc phthalocyanines (ZnPc) reported enhancement in electron mobility due to fluorination. We present a theoretical study of the charge transfer and optical properties of functionalized zinc phthalocyanines (XZnPc, with X = F16, Cl16, Br16, I8, and (CN)8) within the framework of the density functional theory. Substitutions with electron‐withdrawing groups at the peripheral sites of ZnPc was found to lower both EHOMO and ELUMO in the compounds. Computed values of electron affinity (EA) > 3 eV in all XZnPcs indicated effective electron injection inferring enhanced n‐type characteristics and air stability in these compounds. However, cyanation ((CN)8), as compared to the other EWGs, is found to enhance the electron mobility more prominently in the compound. In addition, studied optical absorption spectra of all XZnPc compounds at different exchange‐correlation functionals such as B3LYP, PBE0, CAM‐B3LYP, wB97xD, M06, and M06‐2X exhibited Q‐band in visible region (∼600‐700 nm) and B‐band (Soret) in ultraviolet (∼300‐400 nm) region, and a few shows an N‐band below 300 nm. Upon functionalization, the B‐band and Q‐band maxima show bathochromic shift both in gas phase and dimethyl sulfoxide. All these optical absorptions were found to be prototypical in nature, and the spectra are assigned to π→π∗ character.

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A modified two-sphere model for solvent reorganization energy in electron transfer

Cited by 21 publications

References 38 publications

Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy

Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy

Highly Polarized Coumarin Derivatives Revisited: Solvent‐Controlled Competition Between Proton‐Coupled Electron Transfer and Twisted Intramolecular Charge Transfer

Charge transport and prototypical optical absorptions in functionalized zinc phthalocyanine compounds: A density functional study

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