Quantitative Structure−Stability Relationships for Oxides and Peroxides of Potential Atmospheric Significance
Quantitative Structure−Stability Relationships for Oxides and Peroxides of Potential Atmospheric Significance
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具有潜在大气意义的氧化物和过氧化物的定量结构-稳定性关系
DOI：
10.1021/jp952763s
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
A. Colussi
中科院分区：
文献类型：
--
作者：
M. A. Grela;A. Colussi
对气相物种的最新实验和从头算热化学数据的严格分析表明：(1)简单氧化物之间的等键歧化反应，1/2XOX+1/2YOY↔XOY，以及那些单独涉及氧化物1/2XOOX+1/2YOOY↔XOOY的反应，几乎是热中和的(ΔHR=0±3千卡/摩尔)，但氧化物与过氧物之间的交换反应，XOX+YOOY↔YOY+XOOX，一般不是，(2)过氧化键对H-，C-，N-，N-氧化物形成热的贡献的键加和性值BAV[X−(O−O)−X]Sχ(X)的S和(3)半经验评估(MOPAC)热化学数据集，即使在绝对值不准确的情况下，也符合这些规则。这些发现恰好为快速和系统地评估新型氧化物和过氧化物的稳定性提供了基础。在这篇文章中，我们简要地介绍了可能在陆地大气中形成的物种。
A critical analysis of the most recent experimental and ab initio thermochemical data on gas-phase species reveals that (1) isodesmic metathetical reactions among simple oxides, 1/2XOX + 1/2YOY ↔ XOY, and those exclusively involving peroxides 1/2XOOX + 1/2YOOY ↔ XOOY, are nearly thermoneutral (ΔHr = 0 ± 3 kcal/mol), but exchange reactions between oxides and peroxides, XOX + YOOY ↔ YOY + XOOX, are generally not, (2) bond additivity values BAV[X−(O−O)−X]'s for the contributions of the peroxide bond to the heats of formation of H-, C-, N-, S-, F-, and Cl-containing peroxides decrease linearly with Pauling electronegativities χ(X)'s and (3) semiempirically evaluated (MOPAC) thermochemical datasets, even when inaccurate in absolute terms, are internally consistent with such rules. These findings happen to provide the basis for the rapid and systematic assessment of the stability of novel oxides and peroxides. In this paper, that focuses on species that could be formed in the terrestrial atmosphere, we briefly ...