• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The Journal of Chemical Physics >Geometry optimization based on linear response free energy with quantum mechanical/molecular mechanical method: Applications to Menshutkin-type and Claisen rearrangement reactions in aqueous solution
【24h】

Geometry optimization based on linear response free energy with quantum mechanical/molecular mechanical method: Applications to Menshutkin-type and Claisen rearrangement reactions in aqueous solution

机译：量子力学/分子力学方法基于线性响应自由能的几何优化：在水溶液中的孟舒金型和克莱森重排反应中的应用

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 authors present a method based on a linear response theory that allows one to optimize the geometries of quantum mechanical/molecular mechanical (QM/MM) systems on the free energy surfaces. Two different forms of linear response free energy functionals are introduced, and electronic wave functions of the QM region, as well as the responses of electrostatic and Lennard-Jones potentials between QM and MM regions, are self-consistently determined. The covariant matrix relating the QM charge distribution to the MM response is evaluated by molecular dynamics (MD) simulation of the MM system. The free energy gradients with respect to the QM atomic coordinates are also calculated using the MD trajectory results. They apply the present method to calculate the free energy profiles of Menshutkin-type reaction of NH3 with CH3Cl and Claisen rearrangement of allyl vinyl ether in aqueous solution. For the Menshutkin reaction, the free energy profile calculated with the modified linear response free energy functional is in good agreement with that by the free energy perturbation calculations. They examine the nonequilibrium solvation effect on the transmission coefficient and the kinetic isotope effect for the Claisen rearrangement. (c) 2007 American Institute of Physics.
机译：作者提出了一种基于线性响应理论的方法，该方法可以优化自由能表面上的量子力学/分子力学（QM / MM）系统的几何形状。介绍了两种不同形式的线性响应自由能泛函，并确定了QM区域的电子波函数以及QM和MM区域之间的静电势和Lennard-Jones电势的响应。通过MM系统的分子动力学（MD）仿真来评估将QM电荷分布与MM响应相关的协变矩阵。还使用MD轨迹结果来计算相对于QM原子坐标的自由能梯度。他们应用本方法计算了NH3与CH3Cl的Menshutkin型反应的自由能谱以及水溶液中烯丙基乙烯基醚的克莱森重排。对于Menshutkin反应，使用改进的线性响应自由能函数计算出的自由能曲线与通过自由能扰动计算得出的自由能曲线非常吻合。他们研究了非平衡溶剂化对克莱森重排的透射系数和动力学同位素效应的影响。 （c）2007年美国物理研究所。

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