title: Ab initio investigation on ion-associated species and association process in aqueous Na2SO4 and Na2SO4/MgSO4 solutions.
abstract: In the present paper, the possible ion associated species in pure Na(2)SO(4) and mixed Na(2)SO(4)/MgSO(4) aqueous solutions are investigated via the ab initio method at the HF/6-31+G∗ level. The vibrational v(1)-SO(4)(2-) band is analyzed. For the unhydrated species, when the number of metal ions around the SO(4)(2-) ion is less than 3, the dominating effect to the v(1)-SO(4)(2-) band is the polarization of the cations, while the M-O bonding will be dominating as the number is equal to or more than 3. For the hydrated species, the coordinated structures of the Na(+) ion in all ion pairs are not stable due to the strong effect of the SO(4)(2-) ion but relatively stable in the triple ion (TI) clusters since there are fewer vacant hydration sites around the SO(4)(2-). The v(1)-SO(4)(2-) frequencies are close to that of the hydrated SO(4)(2-) ion in the ion pairs and larger in both Na(2)SO(4) and Na(2)SO(4)/MgSO(4) TI clusters. On the basis of our calculated results, the evolvement of Raman spectra in the Na(2)SO(4)/MgSO(4) droplet with the molar ratio of 1:1 is explained.
authors: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
authors: Hao
authors: H
authors: Zhang
authors: Song
authors: S
authors: Wang
authors: Chia-Chung
authors: CC
authors: Sun
mesh_terms: D008278:Magnesium Sulfate / Q000737:chemistry*; D008958:Models, Molecular; D012996:Solutions; D013431:Sulfates / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D012996:Solutions; D013431:Sulfates; D014867:Water; C012036:sodium sulfate; D008278:Magnesium Sulfate