Dynamical behavior of anion-water and water-water hydrogen bonds in aqueous electrolyte solutions: A molecular dynamics study

被引：177

作者：

Chandra, A ^{[1
]}

机构：

[1] Indian Inst Technol, Dept Chem, Kanpur 208016, Uttar Pradesh, India

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2003年 / 107卷 / 16期

关键词：

D O I：

10.1021/jp022147d

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 dynamics of breaking and structural relaxation of Cl--water, Br--water and water-water hydrogen bonds in aqueous alkali halide solutions are investigated by means of molecular dynamics simulations. The hydrogen bonds are defined by using a set of configurational criteria with respect to the anion(oxygen)oxygen and anion(oxygen)-hydrogen distances and the anion(oxygen)-oxygen -hydrogen angle for an anion(water)-water pair. The results of the hydrogen bond dynamics are obtained for a smaller cutoff and also for a larger cutoff for the angular criterion. In both cases, the dynamics of anion-water hydrogen bonds are found to be slower than that of water-water hydrogen bonds. However, the extent of slowing down is not as great as observed in recent experiments. The relaxation of anion-water hydrogen bonds is found to slow with an increase of ion concentration which is in agreement with the trend observed in experiments. The diffusion coefficients and the orientational relaxation times of water molecules in the vicinity of halide ions and also in the bulk phase are calculated, and the relative changes of these quantities are compared with those of the hydrogen bond dynamics for anion-water and water-water pairs.

引用

页码：3899 / 3906

页数：8

共 64 条

[1]

Allen M. P., 1987, Computer Simulation of Liquids

[2] Dynamical structure of XCl (X = Li, Na, K) aqueous solutions by low-frequency Raman scattering:: relation between 50 cm-1 vibration mode and relaxation mode [J].

Amo, Y ;

Tominaga, Y .

PHYSICA A, 2000, 275 (1-2) :33-47

[3] Hydrogen-bond dynamics near a micellar surface: Origin of the universal slow relaxation at complex aqueous interfaces [J].

Balasubramanian, S ;

Pal, S ;

Bagchi, B .

PHYSICAL REVIEW LETTERS, 2002, 89 (11) :1-115505

[4] Slow orientational dynamics of water molecules at a micellar surface [J].

Balasubramanian, S ;

Bagchi, B .

JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (14) :3668-3672

[5] Slow solvation dynamics near an aqueous micellar surface [J].

Balasubramanian, S ;

Bagchi, B .

JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (50) :12529-12533

[6] Molecular dynamics simulation of electrolyte solutions in ambient and supercritical water .1. Ion solvation [J].

Balbuena, PB ;

Johnston, KP ;

Rossky, PJ .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (07) :2706-2715

[7] THE DISTRIBUTION OF RINGS OF HYDROGEN-BONDED MOLECULES IN A MODEL OF LIQUID WATER [J].

BELCH, AC ;

RICE, SA .

JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (10) :5676-5682

[8] Structure, thermodynamics, and dynamics of the liquid/vapor interface of water/dimethylsulfoxide mixtures [J].

Benjamin, I .

JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (16) :8070-8079

[9]

Berendsen H., 1981, INTERMOLECULAR FORCE, V331, P331, DOI [DOI 10.1007/978-94-015-7658-1_21, 10.1007/978-94-015-7658, DOI 10.1007/978-94-015-7658]

[10] THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS [J].

BERENDSEN, HJC ;

GRIGERA, JR ;

STRAATSMA, TP .

JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (24) :6269-6271

← 1 2 3 4 5 6 7 →