Studies of solvation free energies of methylammoniums and irregular basicity ordering of methylamines in aqueous solution by a combined discrete-continuum model

被引:22
作者
Cao, ZJ
Lin, MH
Zhang, QN
Mo, YR [1 ]
机构
[1] Western Michigan Univ, Dept Chem, Kalamazoo, MI 49008 USA
[2] Xiamen Univ, Dept Chem, State Key lab Phys Chem Solid Surf, Ctr Theoret Chem, Xiamen 361005, Peoples R China
基金
中国国家自然科学基金;
关键词
D O I
10.1021/jp0377127
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 solvation free energies of MenNH4-n+ (n = 0, 1, 2, and 3) have been computed by means of a combined discrete-continuum model, in which the ionic solute and the solvent molecules in the first layers around the hydrogen atoms or protons bonded to the nitrogen atom are treated quantum mechanically and the remaining solvent is simulated by a continuum model. The results show that the discrete-continuum model can predict the solvation free energies of charged species within the chemical accuracy. On the basis of the computed solvation free energies, we further explore the nature of the irregular order in basicity of a series of methylamines in aqueous solution. Analyses reveal that the short-range solute-solvent interactions play a very important role in the inversion of basicity.
引用
收藏
页码:4277 / 4282
页数:6
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共 56 条
[51]  
TOLLENAERE JP, 1978, TETRAHEDRON LETT, P1347
[52]   MOLECULAR-INTERACTIONS IN SOLUTION - AN OVERVIEW OF METHODS BASED ON CONTINUOUS DISTRIBUTIONS OF THE SOLVENT [J].
TOMASI, J ;
PERSICO, M .
CHEMICAL REVIEWS, 1994, 94 (07) :2027-2094
[53]   METHYLAMINES BASICITY CALCULATIONS - IN VACUO AND IN SOLUTION COMPARATIVE-ANALYSIS [J].
TUNON, I ;
SILLA, E ;
TOMASI, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (22) :9043-9048
[54]   ORIGIN OF ALKYL SUBSTITUENT EFFECT IN PROTON AFFINITY OF AMINES, ALCOHOLS, AND ETHERS [J].
UMEYAMA, H ;
MOROKUMA, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (15) :4400-4404
[55]   COMPUTER-SIMULATION OF MOLECULAR-DYNAMICS - METHODOLOGY, APPLICATIONS, AND PERSPECTIVES IN CHEMISTRY [J].
VANGUNSTEREN, WF ;
BERENDSEN, HJC .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1990, 29 (09) :992-1023
[56]   CONTINUUM ELECTROSTATICS IN A COMPUTATIONAL UNIVERSE WITH FINITE CUTOFF RADII AND PERIODIC BOUNDARY-CONDITIONS - CORRECTION TO COMPUTED FREE-ENERGIES OF IONIC SOLVATION [J].
WOOD, RH .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (14) :6177-6187