Experimental and Theoretical Analysis of Photoinduced Electron Transfer: Including the Role of Liquid Structure

نویسندگان

  • S. F. Swallen
  • Kristin Weidemaier
  • H. L. Tavernier
چکیده

Experimental determinations of the dynamics of photoinduced electron transfer from rubrene to duroquinone in three solvents, dibutyl phthalate, diethyl sebacate, and cyclohexanone are presented. Measurements of the donor (rubrene) fluorescence decays were made with time-correlated single-photon counting. The data are analyzed using recent theoretical developments that include important features of the solvent, i.e., the effects of finite molecular volume on local solvent structure and on the mutual donor-acceptor diffusion rates. Inclusion of the liquid radial distribution function (rdf) in the theory accounts for the significant variation of the acceptor concentration near a donor. Because the concentration of acceptors near a donor is substantially greater than the average concentration used in a featureless continuum liquid model, incorporating the rdf is necessary to properly analyze experimental data. Hydrodynamic effects, which slow the rate of donoracceptor approach at short distance, are important and are also included in the theoretical analysis of the data. The data analysis depends on a reasonable model of the rdf. A hard-sphere liquid rdf is shown to be sufficiently accurate by comparing model electron-transfer calculations using a hard-sphere rdf and an rdf from neutronscattering experiments reported in the literature. A method is presented to obtain the hard-sphere parameters needed to calculate the rdf. The method uses a self-consistent determination of the hard-sphere radius and diffusion constant and the solvent self-diffusion constant calculated from the Spernol and Wirtz equation. The Marcus form of the distance-dependent transfer rate is used. For the highest viscosity solvent (dibutyl phthalate), a unique set of the Marcus transfer parameters is obtained. For lower viscosity solvents, the transfer parameters are less well defined, but information on the distance and time dependence of charge separation is still acquired. These experiments, combined with the theoretical analysis, yield the first realistic description of through-solvent photoinduced electron transfer.

برای دانلود رایگان متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Quantum Chemical Modeling of N-(2-benzoylphenyl)oxalamate: Geometry Optimization, NMR, FMO, MEP and NBO Analysis Based on DFT Calculations

In the present work, the quantum theoretical calculations of the molecular structure of the (N-(2-benzoylphenyl) oxalamate has been investigated and are evaluated using Density Functional Theory (DFT). The geometry of the title compound was optimized by B3LYP method with 6-311+G(d) basis set. The theoretical 1H and 13C NMR chemical shift (GIAO method) values of the title compound are calculated...

متن کامل

Bimolecular photoinduced electron transfer reactions in liquids under the gaze of ultrafast spectroscopy.

Because of their key role in many areas of science and technology, bimolecular photoinduced electron transfer reactions have been intensively studied over the past five decades. Despite this, several important questions, such as the absence of the Marcus inverted region or the structure of the primary reaction product, have only recently been solved while others still remain unanswered. Ultrafa...

متن کامل

Theoretical Study of Photoinduced Proton-Coupled Electron Transfer through Asymmetric Salt Bridges

The theoretical study in this paper is based on the experimental result that the rate of photoinduced electron transfer is ∼102 times slower through a donor-(amidinium-carboxylate)-acceptor salt bridge than through the corresponding switched interface donor-(carboxylate-amidinium)-acceptor complex (Kirby, J. P.; Roberts, J. A.; Nocera, D. G. J. Am. Chem. Soc. 1997, 119, 9230). This experimental...

متن کامل

Amine Based CO2 Absorption in Membrane Contactor Using Polyvinyl Pyrrolidone-modified Polysulfone Flat Sheet Membrane: Experimental Study and Mass Transfer Resistance Analysis

Membrane contactor using amine based absorbents is an efficient technology for CO2 separation from gaseous mixtures. A novel porous polysulfone (PSF) flat membrane was prepared via non-solvent phase inversion method. The PSF membrane was modified by adding polyvinyl pyrrolidone (PVP) to the dope solution. The fabricated membrane was used in the serpentine flow field contactor module for CO2 abs...

متن کامل

Computational Study of Chemical Properties of Xylometazoline and the Connected form to Fullerene (C60) as a Medicine Nano Carrier

In this research at the first, xylometazoline hydrochloride drug (XY) and its fullerene connected form (FXY) were optimized. Natural Bond Orbital (NBO) calculations for these compounds were carried out at the B3LYP/6-31G* quantum chemistry level, in the gas phase and the liquid phase. These calculations can be performed at different accuracy levels depending on the aim of the theoretical study....

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 1995