Emergence of Solvent-Separated Na+-Cl- Ion Pair in Salt Water: Photoelectron Spectroscopy and Theoretical Calculations

被引：42

作者：

Hou, Gao-Lei ^{[1
]}

Liu, Cheng-Wen ^{[2
]}

Li, Ren-Zhong ^{[1
]}

Xu, Hong-Guang ^{[1
,3
]}

Gao, Yi Qin ^{[2
]}

Zheng, Wei-Jun ^{[1
,3
]}

机构：

[1] Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China

[2] Peking Univ, Beijing Natl Lab Mol Sci, Inst Theoret & Computat Chem, Coll Chem & Mol Engn, Beijing 100871, Peoples R China

[3] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 01期

基金：

中国国家自然科学基金;

关键词：

CORRELATED MOLECULAR CALCULATIONS; MONTE-CARLO-SIMULATION; GAUSSIAN-BASIS SETS; SODIUM-CHLORIDE; ALKALI-HALIDES; CHARGE SEPARATION; AQUEOUS-SOLUTIONS; INFRARED-SPECTRA; DISSOLUTION; CLUSTERS;

D O I：

10.1021/acs.jpclett.6b02670

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：

Solvation of salts in water is a fundamental physical chemical process, but the underlying mechanism remains unclear. We investigated the contact ion pair (CIP) to solvent-separated ion pair (SSIP) transition in NaCI(H2O) clusters with anion photoelectron spectroscopy and ab initio calculations. It is found that the SSIP type of structures show up at n = 2 for NaCI-(H2O) anions. For neutral NaCI(H2O), the CIP structures are dominant at n < 9. At n = 9-12, the CIP structures and SSIP structures of NaCI(H2O) are nearly degenerate in energy, coincident to the H2O:NaCI molar ratio of NaCI saturated solution and implying that the CIP and SSIP structures can coexist in concentrated solutions. These results are useful for understanding the solvation of salts at the molecular level.

引用

页码：13 / 20

页数：8

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