Probing the dynamics of solvation and structure of the OH- ion in aqueous solution from picosecond transient absorption measurements.

نویسندگان

  • Olivier Poizat
  • Guy Buntinx
چکیده

The reaction of intracomplex proton transfer (44BPY(-.)...HO-H) (R)-->44BPYH(.)+ OH(-) that follows the photoreduction of 4,4'-bipyridine (44BPY) into its anion radical 44BPY(-) in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) is investigated in acetonitrile-water mixtures by using picosecond transient absorption. The dependence of the appearance kinetics of the 44BPYH(.) radical on the water content reveals a highly diffusional proton transfer process that is controlled by the dynamics of solvation of the released hydroxide ion. The results are interpreted on the basis of a two-step mechanism where an intermediate solvation complex (44BPYH(.))OH(-)(H(2)O)(3) is formed first before evolving toward a final four-water hydration structure OH(-)(H(2)O)(4).

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

Thermodynamics of CO2 reaction with methylamine in aqueous solution: A computational study

Separation and capture of carbon dioxide from the flue gas of power plants in order to reduceenvironmental damages has always been of interest to researchers. In this study, aqueous solution ofmethylamine was used as an absorbent for CO2 capture. In order to study this reaction, DensityFunctional Theory (DFT) was employed at the level of B3LYP/6-311++G(d,p) by using theconductor-like polarizabl...

متن کامل

Theoretical calculations of solvation 12-Crown-4 (12CN4) in aqueous solution and its experimental interaction with nano CuSO4

Theoretical study of the electronic structure, and nonlinear optical properties (NLO) analysis of 12-crown-4were done using Density Functional Theory (DFT) evaluations at the B3LYP/6-311G (d,p) level of theory. The optimized structure is nonlinear compound as indicated from the dihedral angles were presented. The calculated EHOMO and ELUMO energies of 12-Crown-4 (12CN4) ca...

متن کامل

Theoretical calculations of solvation 12-Crown-4 (12CN4) in aqueous solution and its experimental interaction with nano CuSO4

Theoretical study of the electronic structure, and nonlinear optical properties (NLO) analysis of 12-crown-4were done using Density Functional Theory (DFT) evaluations at the B3LYP/6-311G (d,p) level of theory. The optimized structure is nonlinear compound as indicated from the dihedral angles were presented. The calculated EHOMO and ELUMO energies of 12-Crown-4 (12CN4) ca...

متن کامل

Probing the transition from hydrophilic to hydrophobic solvation with atomic scale resolution.

Picosecond and femtosecond X-ray absorption spectroscopy is used to probe the changes of the solvent shell structure upon electron abstraction of aqueous iodide using an ultrashort laser pulse. The transient L(1,3) edge EXAFS at 50 ps time delay points to the formation of an expanded water cavity around the iodine atom, in good agreement with classical and quantum mechanical/molecular mechanics...

متن کامل

Ion exchange growth of Zinc Sulfide quantum dots in aqueous solution

We report the growth by ion exchange synthesis of ZnS nanoparticles in MCM-41 matrices using Zn (CH3COO)2 and Na2S starting sources. The final product (ZnS/MCM-41) was characterized by X-ray diffraction (XRD) pattern, transmission electron microscopy (TEM), scanning electron microscopy (SEM), infrared spectrometry (IR) and UV-vis spectroscopy. Its crystalline st...

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:
  • Molecules

دوره 15 5  شماره 

صفحات  -

تاریخ انتشار 2010