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arXiv 2011.08509physics.chem-phphysics.comp-ph
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一种通往激发态的登山策略：小分子的高精度振子强度和偶极矩

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

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

备注：
24 pages (Supp. Mat. available)
发表信息：
J. Chem. Theory Comput. 17, 416 (2021)
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摘要：

这项工作提出了一系列高精度的激发态特性，使用高阶耦合簇（CC）计算进行了一系列的扩散包含基组，以及与实验值进行了广泛的比较。事实上，我们已经计算了主要的基态到激发态跃迁性质，振子强度，以及基态和激发态的偶极矩，考虑了{13}个小分子（硼、氯化氢、水、硫化氢、氟化硼、一氧化碳、二氮、乙烯、甲醛、硫代甲醛、硝酰基、{氟卡宾}和甲硅烷基）。我们系统地包括校正的五元组（CCSDTQP）在CC扩展和外推到完整的基组限制。当可以与实验测量进行比较时，也就是说，当可以找到许多一致的实验数据时，理论通常提供落入激发态性质的实验误差范围内的值。除了完成我们以前的研究重点是过渡能（\textit{J.~Chem.~Theory Comput.} \textbf{14}（2018）4360--4379、\textit{ibid.} ~ \textbf{15}（2019）1939--1956、\textit{ibid.} ~ \textbf{16}（2020）1711--1741和\textit{ibid.} ~ \textbf{16}（2020）3720--3736），这项工作还提供了超精确的偶极子和振荡器强度，可用于未来的理论基准。

英文摘要：

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.

机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。

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