...
  • 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 >Using Constrained Schrodinger Equations to Separate Resonant and Inductive Substituent Effects: A New Methodology for Parametrizing Simple Models in Chemistry
【24h】

Using Constrained Schrodinger Equations to Separate Resonant and Inductive Substituent Effects: A New Methodology for Parametrizing Simple Models in Chemistry

机译：使用约束的薛定inger方程分离共振和感应取代基效应：参数化化学中简单模型的新方法

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

Simple models of chemical phenomena can provide both useful insights and predictive power. These models are parametrized using data on model systems, which are chose to allow the effects of interest to be isolated. Ab initio calculations can provide a useful source of such data. This article explores the use of constrained Schrodinger equations to generate rich sets of ab initio data that can support parametrization of a more diverse set of models than is possible with existing methods. The constraints are used to control the electronic configuration of the model compounds, such that data can be generated on electronic structure-property relationships. The current investigation uses constraints to modulate resonance in substituted benzene compounds. The resulting resonant and nonresonant benzenes are used to parametrize a simple model of inductive and resonant electronic substituent effects, which is similar to the Swain-Lupton substituent-effect model. This parametrization is benchmarked against the standard method of parametrizing such models: fitting inductive and resonant parameters to data from substituted bicyclo[2.2.2]octanes and benzenes. The comparison is made within a consistent model chemistry, as defined by the use of an STO-3G basis and inclusion of correlation via MP2 theory. The parameter sets obtained with the standard and constrained Schrodinger equation methods are very similar and perform equally well at predicting substituent effects in other molecules. The parameter set from the constrained method has a lower correlation between inductive and resonant parameters, suggesting that this method is better at separating these two effects. These results suggest that constrained Schrodinger equation methods can provide a useful means of generating ab initio data for models of electronic structure-property relationships.
机译：简单的化学现象模型可以提供有用的见识和预测能力。使用模型系统上的数据对这些模型进行参数化，选择这些模型以隔离感兴趣的影响。从头算起可以提供此类数据的有用来源。本文探讨了使用受约束的Schrodinger方程生成从头算数据的丰富集合，这些数据可以支持比现有方法更多样化的模型集的参数化。约束条件用于控制模型化合物的电子结构，以便可以根据电子结构-属性关系生成数据。当前的研究使用约束条件来调节取代苯化合物中的共振。所得的共振和非共振苯用于参数化感应和共振电子取代基效应的简单模型，该模型类似于Swain-Lupton取代基效应模型。该参数化是针对参数化此类模型的标准方法进行基准测试的：将感应参数和共振参数拟合到来自取代的双环[2.2.2]辛烷和苯的数据中。根据使用STO-3G基础并通过MP2理论包含相关性的定义，在一致的模型化学中进行比较。用标准的和受约束的薛定methods方程方法获得的参数集非常相似，并且在预测其他分子中的取代基效果方面表现同样出色。约束方法的参数集在电感参数和谐振参数之间具有较低的相关性，这表明该方法在分离这两种效果方面效果更好。这些结果表明，受约束的薛定inger方程方法可以为电子结构-属性关系模型的产生从头算数据提供有用的手段。

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