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Single- and multireference electronic structure calculations for constructing potential energy surfaces
International Reviews in Physical Chemistry ( IF 2.5 ) Pub Date : 2016-06-27 , DOI: 10.1080/0144235x.2016.1195102
Richard Dawes , Steve A. Ndengué

Recent developments in single and multireference electronic structure methods and the approaches suitable to generate ab initio data that may be employed in the construction of global molecular potential energy surfaces are reviewed. The most appropriate, robust, accurate and cost effective strategies are discussed in the context of various applications ranging from cold collisions and weakly interacting clusters, to large amplitude motion in covalently bound molecules, as well as reaction and photodissociation dynamics. The relationships between the types and necessary quantity of ab initio data, and representations through fitting are important, and issues related to symmetry and electronic state degeneracy are mentioned. The impacts of limitations or error in the electronic structure data are discussed in terms of how they are reflected in calculations of spectroscopy, dynamics and kinetics. This discussion includes examples such as the submerged reef feature found along the path to formation of ozone on several published potentials. For that example, a relatively small absolute error in the form of a spurious barrier has profound effects on the dynamics and rates of exchange reactions. The origin of the spurious barrier in ozone and other systems is discussed from an electronic structure standpoint. The effective use of dynamically-weighted state-averaged multireference calculations to obtain robustly convergent global surfaces is detailed.

中文翻译:

用于构建势能面的单参考和多参考电子结构计算

回顾了单参考和多参考电子结构方法的最新发展以及适用于生成可用于构建全局分子势能面的从头算数据的方法。在从冷碰撞和弱相互作用簇到共价结合分子的大振幅运动以及反应和光解动力学等各种应用的背景下,讨论了最合适、稳健、准确和具有成本效益的策略。ab initio 数据的类型和必要数量之间的关系以及通过拟合的表示很重要,并提到了与对称性和电子状态简并相关的问题。电子结构数据中的限制或错误的影响根据它们如何反映在光谱学、动力学和动力学的计算中进行讨论。这个讨论包括一些例子,例如在几个已公布的电位上沿着臭氧形成路径发现的水下珊瑚礁特征。例如,以伪势垒形式出现的相对较小的绝对误差对交换反应的动力学和速率具有深远的影响。从电子结构的角度讨论了臭氧和其他系统中虚假屏障的起源。详细介绍了有效使用动态加权状态平均多参考计算以获得稳健收敛的全局表面。这个讨论包括一些例子,例如在几个已公布的电位上沿着臭氧形成路径发现的水下珊瑚礁特征。例如,以伪势垒形式出现的相对较小的绝对误差对交换反应的动力学和速率具有深远的影响。从电子结构的角度讨论了臭氧和其他系统中虚假屏障的起源。详细介绍了有效使用动态加权状态平均多参考计算以获得稳健收敛的全局表面。这个讨论包括一些例子,例如在几个已公布的电位上沿着臭氧形成路径发现的水下珊瑚礁特征。例如,以伪势垒形式出现的相对较小的绝对误差对交换反应的动力学和速率具有深远的影响。从电子结构的角度讨论了臭氧和其他系统中虚假屏障的起源。详细介绍了有效使用动态加权状态平均多参考计算以获得稳健收敛的全局表面。从电子结构的角度讨论了臭氧和其他系统中虚假屏障的起源。详细介绍了有效使用动态加权状态平均多参考计算以获得稳健收敛的全局表面。从电子结构的角度讨论了臭氧和其他系统中虚假屏障的起源。详细介绍了有效使用动态加权状态平均多参考计算以获得稳健收敛的全局表面。
更新日期:2016-06-27
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