Complex Orbital Calculation of Singlet-Triplet Molecular Oxygen Spacing and its Effect on the Theoretical Investigation of a Large Number of Atmospheric Reactions

机译：单重态-三重态分子氧空间的复轨道计算及其对大量大气反应理论研究的影响

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A large number of gas-phase reactions of atmospheric significance involve molecular oxygen production pathways either through the singlet or the triplet potential energy surfaces. In the investigation of such systems, it has been repeatedly observed that very sophisticated quantum mechanical electronic structure methods fail to produce the correct energy level of singlet ~1Δ O_2. In the present work a series of quantum mechanical calculations of the singlet O_2 (~1Δ) electronic energy are carried out using the complex orbitals methodology at the HF and MP2 levels of theory. It is found that although the Hartree-Fock method considerably underestimates the energy splitting, the MP2 level produces the correct electronic energy and the derived singlet-triplet energy spacing is found to be 22.4 kcal mol~(-1), in excellent agreement with the experimental findings. The consequences of this result in the lowering of the O_2 (~1Δ) production pathways in a large number of atmospheric reactions is discussed in detail.

机译：大量具有大气意义的气相反应涉及通过单重态或三重态势能表面的分子氧产生途径。在研究此类系统时，已经反复观察到，非常复杂的量子力学电子结构方法无法产生正确的单线态〜1ΔO_2能级。在目前的工作中，使用复轨道方法在HF和MP2的理论水平上进行了单重态O_2（〜1Δ）电子能量的一系列量子力学计算。结果发现，尽管Hartree-Fock方法大大低估了能量分裂，但MP2能级产生了正确的电子能量，并且推导的单重态-三重态能量间距为22.4 kcal mol〜（-1），与能量实验结果。详细讨论了这种结果在大量大气反应中降低O_2（〜1Δ）生成途径的后果。

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《Advances in Computational Methods in Sciences and Engineering 2005 vol.4A; Lecture Series on Computer and Computational Sciences; vol.4A》|2005年|P.721-723|共3页
会议地点 Loutraki(GR)
作者
Agnie M. Kosmas; Evangelos Drougas;
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作者单位

Department of Chemistry, Physical Chemistry Sector, University of Ioannina, GR-451 10 Ioannia, Greece;

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会议组织
原文格式 PDF
正文语种 eng
中图分类计算数学的应用;
关键词
singlet oxygen; triplet oxygen; complex orbitals; atmospheric reactions;

机译：单重态氧;三重态氧;复杂轨道;大气反应;

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Complex Orbital Calculation of Singlet-Triplet Molecular Oxygen Spacing and its Effect on the Theoretical Investigation of a Large Number of Atmospheric Reactions

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