Rigorous Non-Born-Oppenheimer Variational Calculations of H3+ and Its Isotopomers

亚利桑那大学的Ludwik Adamowicz获得了化学系理论与计算化学项目的奖励，用于研究开发和实施使用显式相关多粒子高斯基函数（ECGs）对H3+及其同位素进行直接、严格、变分非born - oppenheimer（非bo）计算的方法。该项目有两个重点。首先是三核分子体系非bo计算理论模型的正式建立和理论的计算实现。二是应用该方法研究了H3+及其同位素体的旋振谱。提出的方法是第一个描述在非bo背景下的激发态旋转振动的三原子系统。该项目的更广泛影响包括提高分子量子力学在描述三原子系统的旋转振动特性方面的预测能力。由此产生的新能力将首次允许在没有BO近似限制的情况下考虑化学反应过程，预计将对所有化学产生广泛的影响。

Ludwik Adamowicz of the University of Arizona is supported by an award from the Theoretical and Computational Chemistry program within the Division of Chemistry for research on the development and implementation of methods for carrying out direct, rigorous, variational non-Born-Oppenheimer (non-BO) calculations for H3+ and its isotopomers using explicitly correlated multi-particle Gaussian basis functions (ECGs). The project has two main foci. The first is the formal development of the theoretical model for non-BO calculations of three-nucleus molecular systems and the computational implementation of the theory. The second is the application of the method to study the rovibrational spectra of H3+ and its isotopomers. The proposed approach is the first to describe triatomic systems in excited rovibrational states in a non-BO context. Broader impacts of the project include the elevation of the predictive capabilities of molecular quantum mechanics in describing rovibrational properties of triatomic systems. The new capabilities which will result will allow, for the first time, consideration of chemical reaction processes without the confines of the BO approximation and are expected to have a broad impact on all of Chemistry.