Hollas Daniel, Curchod Basile F E
Centre for Computational Chemistry, School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, United Kingdom.
J Phys Chem A. 2024 Oct 3;128(39):8580-8590. doi: 10.1021/acs.jpca.4c05174. Epub 2024 Sep 18.
Characterizing the photolysis processes undergone by transient volatile organic compounds (VOCs) in the troposphere requires the knowledge of their photoabsorption cross-section-quantities often challenging to determine experimentally, particularly due to the reactivity of these molecules. We present a computational tool coined AtmoSpec, which can predict a quantitative photoabsorption cross-section for volatile organic compounds by using computational photochemistry. The user enters the molecule of interest as a SMILES code and, after selecting a level of theory for the electronic structure (and waiting for the calculations to take place), is presented with a photoabsorption cross-section for the low-energy conformers and an estimate of the photolysis rate coefficient for different standardized actinic fluxes. More specifically, AtmoSpec is an automated workflow for the nuclear ensemble approach, an efficient technique to approximate the absolute intensities and excitation wavelengths of a photoabsorption cross-section for a molecule in the gas phase of interest in atmospheric chemistry and astrochemistry. This work provides background information on the nuclear ensemble approach, a guided example of a typical AtmoSpec calculation, details about the architecture of the code, and the current limitations and future developments of this tool.
表征对流层中瞬态挥发性有机化合物(VOCs)所经历的光解过程,需要了解它们的光吸收截面——这些量通常在实验上难以确定,特别是由于这些分子具有反应活性。我们提出了一种名为AtmoSpec的计算工具,它可以通过计算光化学预测挥发性有机化合物的定量光吸收截面。用户以SMILES代码输入感兴趣的分子,在选择电子结构的理论水平(并等待计算完成)后,会得到低能构象体的光吸收截面以及针对不同标准化光化通量的光解速率系数估计值。更具体地说,AtmoSpec是核系综方法的自动化工作流程,这是一种用于近似大气化学和天体化学中感兴趣的气相分子光吸收截面的绝对强度和激发波长的有效技术。这项工作提供了关于核系综方法的背景信息、典型AtmoSpec计算的示例指南、代码架构的详细信息以及该工具当前的局限性和未来发展方向。