جهت دسترسی به کاربرگه ی زیر، از این لینک استفاده کنید. http://dl.pgu.ac.ir/handle/10023/1751
Title: Oxygen exchange in uranyl hydroxide via two "nonclassical" ions
Keywords: Density-functional theory;1st-principles molecular-dynamics;Polarizable continuum model;Main-group thermochemistry;Aqueous-solution;Noncovalent interactions;Free-energy;Basis-sets;AB-initio;Complexes;QD Chemistry;QD
Issue Date: 19-Apr-2010
Description: A recently proposed pathway for the scrambling of axial (uranyl) and equatorial 0 atoms in [UO2(OH)4]2- (1) is refined using Car-Parrinello molecular dynamics (CPMD) simulations in an explicit solvent (water) and with model counterions (NH4+). According to constrained CPMD/BLYP simulations and thermodynamic integration, 1 can be deprotonated to [UO3(OH)3]3- with a T-shaped UO3 group (Delta A = 7.1 kcal/mol), which in turn can undergo a solvent-assisted proton transfer via a cis-[UO2(OH)4]2-center dot OH- complex and a total overall barrier of Delta A(double dagger) = 12.5 kcal/mol. According to computed relative energies of trans- and cis-[UO2(OH)4]2- in the gas phase and in a polarizable continuum, "pure" functionals such as BLYP underestimate this overall barrier somewhat, and estimates of Delta A(double dagger) approximate to 16 and 17 kcal/mol are obtained at the B3LYP and CCSD(T) levels, respectively, in excellent agreement with the experiment.;Postprint;Peer reviewed
URI: http://dx.doi.org/10.1021/ic902508z
Other Identifiers: Buehl , M & Schreckenbach , G 2010 , ' Oxygen exchange in uranyl hydroxide via two "nonclassical" ions ' Inorganic Chemistry , vol 49 , no. 8 , pp. 3821-3827 . DOI: 10.1021/ic902508z
0020-1669
PURE: 5310792
PURE UUID: 7ebc67e1-ebab-493e-ac0a-f99b177b1300
WOS: 000276556900037
Type Of Material: OTHER
Appears in Collections:Chemistry (School of)

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