Ligand effect on uranium isotope fractionations caused by nuclear volume effects: An ab initio relativistic molecular orbital study

被引：27

作者：

Abe, Minori ^{[1
]}

Suzuki, Tatsuya ^{[2
]}

Fujii, Yasuhiko ^{[2
]}

Hada, Masahiko ^{[1
]}

Hirao, Kimihiko ^{[3
]}

机构：

[1] Tokyo Metropolitan Univ, Dept Chem, Grad Sch Sci, Hachioji, Tokyo 1920397, Japan

[2] Tokyo Inst Technol, Nucl Reactors Res Lab, Meguro Ku, Tokyo 1528550, Japan

[3] RIKEN, Next Generat Mol Theory Unit, Wako, Saitama 3510198, Japan

来源：

JOURNAL OF CHEMICAL PHYSICS | 2010年 / 133卷 / 04期

关键词：

CONSISTENT-FIELD CALCULATIONS; GAUSSIAN-BASIS SETS; ANO BASIS-SETS; WAVE-FUNCTIONS; HARTREE-FOCK; DEPENDENCE;

D O I：

10.1063/1.3463797

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：

We have calculated the nuclear volume term (ln K-nv) of the isotope fractionation coefficient (epsilon) between U-235-U-238 isotope pairs by considering the effect of ligand coordination in a U(IV)-U(VI) reaction system. The reactants were modeled as [UO2Cl3](-) and [UO2Cl4](2-) for U(VI), and UCl4 for U(IV). We adopted the Dirac-Coulomb Hartree-Fock method with the Gaussian-type finite nucleus model. The result obtained was ln K-nv=0.001 90 at 308 K, while the experimentally estimated value of ln K-nv is 0.002 24. We also discuss how the ligand affects the value of ln K-nv, especially for the various structures of different compounds, and different ligands within the halogen ion series (F, Cl, and Br). (C) 2010 American Institute of Physics. [doi:10.1063/1.3463797]

引用

页数：5

共 26 条

[1] A four-index transformation in Dirac's four-component relativistic theory [J].

Abe, M ;

Yanai, T ;

Nakajima, T ;

Hirao, K .

CHEMICAL PHYSICS LETTERS, 2004, 388 (1-3) :68-73

[2] An ab initio molecular orbital study of the nuclear volume effects in uranium isotope fractionations (vol 129, 164309, 2008) [J].

Abe, Minori ;

Suzuki, Tatsuya ;

Fujii, Yasuhiko ;

Hada, Masahiko ;

Hirao, Kimihiko .

JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (11)

[3] An ab initio molecular orbital study of the nuclear volume effects in uranium isotope fractionations [J].

Abe, Minori ;

Suzuki, Tatsuya ;

Fujii, Yasuhiko ;

Hada, Masahiko ;

Hirao, Kimihiko .

JOURNAL OF CHEMICAL PHYSICS, 2008, 129 (16)

[4] An ab initio study based on a finite nucleus model for isotope fractionation in the U(III)-U(IV) exchange reaction system [J].

Abe, Minori ;

Suzuki, Tatsuya ;

Fuji, Yasuhiko ;

Hada, Masahiko .

JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (14)

[5] Mass-dependent and -independent fractionation of Hg isotopes by photoreduction in aquatic systems [J].

Bergquist, Bridget A. ;

Blum, Joel D. .

SCIENCE, 2007, 318 (5849) :417-420

[6] Nuclear size and shape effects in chemical reactions. Isotope chemistry of the heavy elements [J].

Bigeleisen, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (15) :3676-3680

[7] Relativistic Gaussian basis sets for the elements K-Uuo [J].

Faegri, K .

THEORETICAL CHEMISTRY ACCOUNTS, 2001, 105 (03) :252-258

[8]

Frisch M., 2004, GAUSSIAN 03 REVISION, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014

[9] Nuclear field vs. nucleosynthetic effects as cause of isotopic anomalies in the early Solar System [J].

Fujii, Toshiyuki ;

Moynier, Frederic ;

Albarede, Francis .

EARTH AND PLANETARY SCIENCE LETTERS, 2006, 247 (1-2) :1-9

[10] Temperature dependence of isotope effects in uranium chemical exchange reactions [J].

Fujii, Yasuhiko ;

Higuchi, Nobuhiko ;

Haruno, Yoshio ;

Nomura, Masao ;

Suzuki, Tastuya .

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY, 2006, 43 (04) :400-406

← 1 2 3 →