A theoretical study of uranyl solvation: Explicit modelling of the second hydration sphere by quantum mechanical methods

被引:53
作者
Siboulet, B. [1 ]
Marsden, C. J.
Vitorge, P.
机构
[1] CEA, DEN, DRCP, SCPS, F-30207 Bagnols Sur Ceze, France
[2] Univ Toulouse 3, CNRS, Phys Quant Lab, UMR 5626, F-31062 Toulouse 4, France
[3] CEA Saclay, LSRM, SECR, DPC,DEN,UMR 8587, F-91191 Gif Sur Yvette, France
关键词
uranyl; DFT; solvation; ab initio;
D O I
10.1016/j.chemphys.2006.02.006
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The inclusion of an explicit second sphere in the hydration of the uranyl ion is investigated by DFT. We study model complexes that contain two water molecules in the second sphere hydrogen-bonded to each water molecule in the first. Compared with single-sphere models, significant changes are observed for the uranium-water first-sphere distance, the uranium-"yl" oxygen distance and the uranyl stretching vibrational frequencies. For each of these observables, agreement with experiment is improved with our new model. Charge transfer to uranyl is substantially enhanced when the second hydration sphere is present. Effects of third and subsequent hydration spheres appear to be small, but the influence of water molecules linked to the apical oxygens by a hydrogen-bonding network is probably not negligible. Models based on a polarizable continuum are less satisfactory, particularly for the vibrational frequencies. The uranyl stretching frequencies are highly correlated with charge transfer from water molecules to the "yl" oxygen atoms and with the uranyl bond length. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:289 / 296
页数:8
相关论文
共 41 条
[21]   QM/MM study of aqueous solvation of the uranyl fluoride [UO2F2-4] complex [J].
Infante, I ;
Visscher, L .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 2004, 25 (03) :386-392
[22]   Theoretical studies of the actinides:: method calibration for the UO22+ and PuO22+ ions [J].
Ismail, N ;
Heully, JL ;
Saue, T ;
Daudey, JP ;
Marsden, CJ .
CHEMICAL PHYSICS LETTERS, 1999, 300 (3-4) :296-302
[23]  
ISMAIL N, 2000, ETUDE THEORIQUE ION
[24]   ENERGY-ADJUSTED PSEUDOPOTENTIALS FOR THE ACTINIDES - PARAMETER SETS AND TEST CALCULATIONS FOR THORIUM AND THORIUM MONOXIDE [J].
KUCHLE, W ;
DOLG, M ;
STOLL, H ;
PREUSS, H .
JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (10) :7535-7542
[25]   Temperature-dependent hydrogen-bond geometry in liquid water [J].
Modig, K ;
Pfrommer, BG ;
Halle, B .
PHYSICAL REVIEW LETTERS, 2003, 90 (07) :4
[26]   Role of solvation in the reduction of the uranyl dication by water:: A density functional study [J].
Moskaleva, LV ;
Krüger, S ;
Spörl, A ;
Rösch, N .
INORGANIC CHEMISTRY, 2004, 43 (13) :4080-4090
[27]   Experimental coordination environment of uranyl(VI) in aqueous solution [J].
Neuefeind, J ;
Soderholm, L ;
Skanthakumar, S .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (14) :2733-2739
[28]   AQUEOUS URANIUM COMPLEXES .2. RAMAN-SPECTROSCOPIC STUDY OF THE COMPLEX-FORMATION OF THE DIOXOURANIUM(VI) ION WITH A VARIETY OF INORGANIC AND ORGANIC-LIGANDS [J].
NGUYENTRUNG, C ;
BEGUN, GM ;
PALMER, DA .
INORGANIC CHEMISTRY, 1992, 31 (25) :5280-5287
[29]  
ODA Y, 2001, J NUCL FUEL CYCLE EN, V7, P41
[30]   Generalized gradient approximation for the exchange-correlation hole of a many-electron system [J].
Perdew, JP ;
Burke, K ;
Wang, Y .
PHYSICAL REVIEW B, 1996, 54 (23) :16533-16539