...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >New Stress Test for Ring Polymer Molecular Dynamics: Rate Coefficients of the O(P-3) + HCl Reaction and Comparison with Quantum Mechanical and Quasiclassical Trajectory Results
【24h】

New Stress Test for Ring Polymer Molecular Dynamics: Rate Coefficients of the O(P-3) + HCl Reaction and Comparison with Quantum Mechanical and Quasiclassical Trajectory Results

机译：环聚合物分子动力学的新应力测试：o（p-3）+ HCl反应的速率系数和量子力学和拟血管轨迹结果的比较

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

In the past decade, ring polymer molecular dynamics (RPMD) has emerged as a very efficient method to determine thermal rate coefficients for a great variety of chemical reactions. This work presents the application of this methodology to study the O(P-3) + HCl reaction, which constitutes a stringent test for any dynamical calculation due to rich resonant structure and other dynamical features. The rate coefficients, calculated on the (3)A' and (3)A '' potential energy surfaces (PESs) by Ramachandran and Peterson [J. Chem. Phys. 2003, 119, 9590], using RPMD and quasiclassical trajectories (QCT) are compared with the existing experimental and the quantum mechanical (QM) results by Xie et al. [J. Chem. Phys. 2005 122, 014301]. The agreement is very good at T > 600 K, although RPMD underestimates rate coefficients by a factor between 4 and 2 in the 200-500 K interval. The origin of these discrepancies lies in the large contribution from tunneling on the (3)A '' PES, which is enhanced by resonances due to quasibound states in the van der Waals wells. Although tunneling is fairly well accounted for by RPMD even below the crossover temperature, the effect of resonances, a long-time effect, is not included in the methodology. At the highest temperatures studied in this work, 2000-3300 K, the RPMD rate coefficients are somewhat larger than the QM ones, but this is shown to be due to limitations in the QM calculations and the RPMD are believed to be more reliable.
机译：在过去的十年中，环聚合物分子动力学（RPMD）作为确定各种化学反应的热速率系数的非常有效的方法。该工作介绍了该方法的应用，研究O（P-3）+ HCl反应，其构成严格的试验，这是由于丰富的谐振结构和其他动态特征导致的任何动态计算。 ramachandran和peterson的（3）A'和（3）潜在能量表面（PES）计算的速率系数[J.化学。物理。将使用RPMD和Quasiclassical轨迹（QCT）与Xie等人的现有实验和量子机械（QM）结果进行比较2003,119,9590]。 [J.化学。物理。 2005年122,014301]。虽然RPMD在200-500K间隔内低估了速度系数，但rpmd非常良好，尽管RPMD低估了速度系数。这些差异的起源在于（3）A'PE的隧道隧道的巨大贡献，这通过van der Waals井中的Quasibound状态引起的共振增强。尽管甚至低于交叉温度，但隧道的隧道相当占RPMD，但共振的效果，长时间效果不包括在方法中。在这项工作中研究的最高温度下，2000-3300 k，RPMD速率系数略大于QM，但是由于QM计算的限制，据信RPMD更加可靠。

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