论文标题

激发状态的登山策略:高度准确的振荡器强度和小分子的偶极矩

A Mountaineering Strategy to Excited States: Highly-Accurate Oscillator Strengths and Dipole Moments of Small Molecules

论文作者

Chrayteh, Amara, Blondel, Aymeric, Loos, Pierre-François, Jacquemin, Denis

论文摘要

这项工作介绍了一系列使用一系列包含基集的扩散集进行的高阶耦合群集(CC)计算获得的一系列高度精确的激发态性能,并与实验值进行了广泛的比较。实际上,我们已经计算了主要的启用过渡特性,振荡器的强度以及地面和激发型偶极矩,考虑{13}小分子(Hydredoboron,Hydridoboron,Hydridoboron,氯化氢,水,水,氢,硫化物,硫化物,硫化物,硼酸硝基氧基,{氟化合物}和甲硅烷基)。我们系统地包括在CC扩展中校正到五重奏(CCSDTQP),然后外推到完整的基集限制。当可能与实验测量值进行比较时,也就是说,当发现许多一致的实验数据时,理论通常提供属于激发态性能的实验误差栏内的值。除了完成我们以前的研究之外,重点是过渡能量(\ textIt {J.〜Chem。 (2020)1711--1741和\ textit {ibid。}〜\ textbf {16}(2020)3720--3736),这项工作还提供了超精度的偶极子和振荡器强度,可以将来用于将来的理论基准。

This work presents a series of highly-accurate excited-state properties obtained using high-order coupled-cluster (CC) calculations performed with a series of diffuse containing basis sets, as well as extensive comparisons with experimental values. Indeed, we have computed both the main ground-to-excited transition property, the oscillator strength, as well as the ground- and excited-state dipole moments, considering {thirteen} small molecules (hydridoboron, hydrogen chloride, water, hydrogen sulfide, boron fluoride, carbon monoxide, dinitrogen, ethylene, formaldehyde, thioformaldehyde, nitroxyl, {fluorocarbene}, and silylidene). We systematically include corrections up to the quintuple (CCSDTQP) in the CC expansion and extrapolate to the complete basis set limit. When comparisons with experimental measurements are possible, that is, when a number of consistent experimental data can be found, theory typically provides values falling within the experimental error bar for the excited-state properties. Besides completing our previous studies focussed on transition energies (\textit{J.~Chem.~Theory Comput.} \textbf{14} (2018) 4360--4379, \textit{ibid.}~\textbf{15} (2019) 1939--1956, \textit{ibid.}~\textbf{16} (2020) 1711--1741, and \textit{ibid.}~\textbf{16} (2020) 3720--3736), this work also provides ultra-accurate dipoles and oscillator strengths that could be employed for future theoretical benchmarks.

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