Evaluating the Importance of Conformers for Understanding the Vacuum-Ultraviolet Spectra of Oxiranes: Experiment and Theory.

IF 2.7 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry A Pub Date : 2024-12-19 Epub Date: 2024-12-06 DOI:10.1021/acs.jpca.4c04391
Ian T Beck, Erica C Mitchell, Annabelle Webb Hill, Justin M Turney, Brandon Rotavera, Henry F Schaefer
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引用次数: 0

Abstract

Vacuum-ultraviolet (VUV) absorption spectroscopy enables electronic transitions that offer the unambiguous identification of molecules. As target molecules become more complex, multifunctional species present a great challenge to both experimental and computational spectroscopy. This research reports both experimental and theoretical studies of oxiranes. Computationally, the nuclear ensemble approach has been used to accurately predict experimental spectra for a variety of molecules. However, this approach incurs great computational cost, as ensembles generally consist of thousands of geometries. The present study aims to drastically reduce the ensemble by evaluating the significance of the conformers to the predicted spectra. This approach was applied to 11 substituted oxiranes using the Conformer Rotamer Ensemble Sampling Tool (CREST) of Grimme to generate an ensemble of unique conformers determined by their Boltzmann populations. Five TD-DFT functionals (BMK, CAM-B3LYP, M06-2X, MN15, ωB97X-D) and EOM-CCSD were used to simulate the spectrum of each substituted oxirane ensemble. Computed spectra were then compared to the experiment using both qualitative and quantitative metrics. Based on these metrics, it was observed that certain conformers may not be necessary to characterize this set of oxiranes despite the temperature (323 K) of the experiment. A single conformer can then be used with TD-DFT and EOM-CCSD to replicate the experimental spectra of these medium-sized combustion species.

评价构象对理解氧环烷真空紫外光谱的重要性:实验与理论。
真空紫外(VUV)吸收光谱使电子跃迁提供分子的明确鉴定。随着靶分子的日益复杂,多功能性物质对实验和计算光谱学都提出了巨大的挑战。本研究报告了氧环烷的实验和理论研究。计算上,核系综方法已被用来准确地预测各种分子的实验光谱。然而,这种方法产生了巨大的计算成本,因为集成通常由数千个几何形状组成。本研究的目的是通过评估构象对预测光谱的重要性来大幅减少系综。该方法应用于11个取代的氧烷,使用Grimme的构象旋转体集合采样工具(CREST),生成由其玻尔兹曼种群决定的独特构象集合。利用5个TD-DFT泛函(BMK、CAM-B3LYP、M06-2X、MN15、ωB97X-D)和EOM-CCSD模拟了各取代氧环系综的光谱。然后使用定性和定量指标将计算光谱与实验进行比较。根据这些指标,可以观察到,尽管实验温度(323 K),某些构象可能不是表征这组氧环烷所必需的。一个单一的构象可以与TD-DFT和EOM-CCSD一起使用,以复制这些中等燃烧物种的实验光谱。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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