RISM-SCF-SEDDStudy on the Symmetry Breaking ofCarbonate and Nitrate Anions in AqueousSolution
RISM-SCF-SEDDStudy on the Symmetry Breaking ofCarbonate and Nitrate Anions in AqueousSolution
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RISM-SCF-SEDDS水溶液中碳酸根和硝酸根阴离子对称性破缺的研究
DOI：
10.1021/jp101700d
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发表时间：
2010
期刊：
影响因子：
3.3
通讯作者：
Hirofumi Sato,Shigeyoshi Sakaki
中科院分区：
文献类型：
--
作者：
Viwat Vchirawongkwin;Hirofumi Sato,Shigeyoshi Sakaki
采用参考相互作用位模型自洽场空间电子密度分布（RISM-SCF-SEDD）方法研究了气相和溶液中碳酸根和硝酸根阴离子的平面性。计算优化的几何形状和溶剂化结构与衍射数据进行了比较。在溶液相中，碳酸根阴离子的对称性由D3 h变为C3 v，而硝酸根阴离子的平面性仍保持不变。这与实验知识完全一致。利用经典静电模型对对称性破缺的机理进行了解释。应该强调的是，对称性破缺不仅通过特定的溶剂分子附着到离子上发生，而且通过无限数量的溶剂分子和离子之间的整体静电相互作用发生。
The planarity of carbonate and nitrate anions was investigated in the gas and solution phases by means of the reference interaction site model self-consistent field spatial electron density distribution (RISM-SCF-SEDD) method. The computed optimized geometries and solvation structures are compared with the diffraction data. In the solution phase, the symmetry of carbonate anion is changed fromD3htoC3v, whereas the planarity of nitrate anion is still retained. These are fully consistent with experimental knowledge. The classical electrostatic model was also utilized to elucidate the mechanism of the symmetry breaking. It should be emphasized that the symmetry breaking occurs not only by a specific solvent molecule attaching to the ion but by an overall electrostatic interaction between the infinite number of solvent molecules and the ion.