...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >Study of the N-H … O=C proton transfer reaction in aqueous solution using classical free energy curves
【24h】

Study of the N-H … O=C proton transfer reaction in aqueous solution using classical free energy curves

机译：利用经典自由能曲线研究N-H…O = C质子在水溶液中的转移反应

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The classical free energy surfaces of the reactive and product states involved in the proton transfer reaction of the N-H … O=C molecular association in aqueous solution were obtained by means of molecular dynamics simulations using ab initio MP2-CP potentials. The values of the reaction free energy (ΔG = -1.53 kJ mol~(-1), which is opposed to the nonspontaneous character of the reaction in the gas phase) and the rate constant (k~(TST) = 7.92 * 10~(110 s~(-1)) of the process show that viability of this proton transfer in aqueous medium. The change in spontaneity due to the surrounding water reflects a major redistribution of the solvent (ΔG_r = 14.18 kJ mol~(-1)), which leads to a decrease of the energy barrier to a value of ΔG~# = 5.05 kJ mol~(-1). Also, the higher solvent force constant and solvent frequency derived from the free energy curve associated with the non-transferred proton system (k_R = 4.01 * 10~(-4) cm and v_R = 10.13 ps~(-1)) reflect a weakening of the water-water interactions when the solute has the transferred proton.
机译：通过使用从头算的MP2-CP势进行分子动力学模拟，获得了水溶液中N-H…O = C分子缔合的质子转移反应所涉及的反应态和产物态的经典自由能面。反应自由能值（ΔG= -1.53​​ kJ mol〜（-1），与气相反应的非自发特性相反）和速率常数（k〜（TST）= 7.92 * 10〜该过程（110 s〜（-1））表明该质子在水性介质中转移的可行性，周围水引起的自发性变化反映了溶剂的主要重新分布（ΔG_r= 14.18 kJ mol〜（-1））。 ），导致能垒减小至ΔG〜＃= 5.05 kJ mol〜（-1）。此外，较高的溶剂力常数和溶剂频率由与未转移相关的自由能曲线得出质子系统（k_R = 4.01 * 10〜（-4）cm和v_R = 10.13 ps〜（-1））反映了溶质具有转移质子时水-水相互作用的减弱。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号