Mechanism of water exchange in aqueous uranyl(VI) ion.: A density functional molecular dynamics study

被引：55

作者：

Bühl, M ^{[1
]}

Kabrede, H ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany

来源：

INORGANIC CHEMISTRY | 2006年 / 45卷 / 10期

关键词：

D O I：

10.1021/ic060156l

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Constrained Car-Parrinello molecular dynamics simulations and thermodynamic integration have been performed for an associative pathway of water exchange between aqueous [UO2(OH2)(5)](2+) and bulk water. The simulated free energy of activation for this process, 6.7 kcal mol(-1), is significantly lower than that computed for a purely dissociative mechanism, 10.8 kcal mol(-1). Because the transient hexahydrate is indicated to have no chemically significant lifetime, the exchange mechanism can be classified as associative interchange.

引用

收藏

页码：3834 / 3836

页数：3

相关论文

共 31 条

[1] A DENSITY-FUNCTIONAL STUDY OF CHEMICAL-REACTIONS [J].

ANDZELM, J ;

BAKER, J ;

SCHEINER, A ;

WRINN, M .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1995, 56 (06) :733-746

[2] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[3] Coordination environment of aqueous uranyl(VI) ion [J].

Bühl, M ;

Diss, R ;

Wipff, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (39) :13506-13507

[4]

BUHL M, IN PRESS J AM CHEM S

[5] Theoretical studies of UO2(H2O)n2+,NpO2(H2O)n+, and PuO2(H2O)n2+ complexes (n=4-6) in aqueous solution and gas phase -: art. no. 114309 [J].

Cao, ZJ ;

Balasubramanian, K .

JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (11)

[6] UNIFIED APPROACH FOR MOLECULAR-DYNAMICS AND DENSITY-FUNCTIONAL THEORY [J].

CAR, R ;

PARRINELLO, M .

PHYSICAL REVIEW LETTERS, 1985, 55 (22) :2471-2474

[7] Modeling of uranyl cation-water clusters [J].

Clavaguéra-Sarrio, C ;

Brenner, V ;

Hoyau, S ;

Marsden, CJ ;

Millié, P ;

Dognon, JP .

JOURNAL OF PHYSICAL CHEMISTRY B, 2003, 107 (13) :3051-3060

[8] Investigating actinyl oxo cations by X-ray absorption spectroscopy [J].

Den Auwer, C ;

Simoni, E ;

Conradson, S ;

Madic, C .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2003, (21) :3843-3859

[9] Rates and mechanisms of water exchange of UO22+(aq) and UO2(oxalate)F(H2O)2-:: A variable-temperature 17O and 19F NMR study [J].

Farkas, I ;

Bányai, I ;

Szabó, Z ;

Wahlgren, U ;

Grenthe, I .

INORGANIC CHEMISTRY, 2000, 39 (04) :799-805

[10] The coordination of uranyl in water:: A combined quantum chemical and molecular simulation study [J].

Hagberg, D ;

Karlström, G ;

Roos, BO ;

Gagliardi, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (41) :14250-14256

← 1 2 3 4 →