论文标题
乙醛的气相形成:审查和新的理论计算
Gas-phase formation of acetaldehyde: review and new theoretical computations
论文作者
论文摘要
在所有星际复合物有机分子(ICOM)中,乙醛是最广泛检测到的物种之一。因此,其形成途径的问题是关于天体化学模型的主要兴趣。在本文中,我们对文献和主要天体化学数据库中报告的气相形成路径进行了广泛的综述。四种不同的气相形成路线突出:(1)ch $ _3 $ _3 $ _3 $ + h $^ + $^ + $ / ch $ _3 $ choh $^$^ + $^ + $ + $ + e $^ - $,(2)c $ _2 $ _2 $ _5 $ _5 $ _5 $ + + + + O($^3 $ p) ch $ _3 $ choh + o($^3 $ p)。未通过实验室或理论工程研究路径(2)和(3),在低温和密度状态下对ISM有效。因此,我们进行了新的精确量子化学计算。还进行了低温(7-300 K)的理论动力学研究,采用了RRKM方案。我们确认反应(2)在7-300温度范围内形成乙醛(alpha = 1.21 x 10 $^{ - 10} $ cm $^3 $ s $ s $^{ - 1} $和beta = 0.16)。相反,我们的新计算通过反应(3)(alpha = 1.84,0.67 x 10 $^{ - 13} $ cm $^3 $ s $ s $^{ - 1} $ and beta = -0.07,-07,-0.95)。近期计算表明路径(1)的效率也很低,而路径(4)以前被认为是乙醛形成,并以乙醛为副产品。总而言之,在以上四个路径中,只有两条(2)和(4)是乙醛形成的潜在有效的气相反应途径,我们鼓励天体化学模型仅考虑它们。与天文观测的比较表明,路径(4)实际上可能起着主要作用。
Among all the interstellar complex organic molecules (iCOMs), acetaldehyde is one of the most widely detected species. The question of its formation route(s) is, therefore, of a major interest regarding astrochemical models. In this paper, we provide an extensive review of the gas-phase formation paths that were, or are, reported in the literature and the major astrochemical databases. Four different gas-phase formation routes stand out : (1) CH$_3$OCH$_3$ + H$^+$ / CH$_3$CHOH$^+$ + e$^-$, (2) C$_2$H$_5$ + O($^3$P), (3) CH$_3$OH + CH and (4) CH$_3$CH$_2$OH + OH / CH$_3$CHOH + O($^3$P). Paths (2) and (3) were not studied neither via laboratory or theoretical works in the low temperature and density regime valid for the ISM. Thus, we carried out new accurate quantum chemistry computations. A theoretical kinetics study at low temperatures (7-300 K), adopting the RRKM scheme, was also performed. We confirm that reaction (2) is efficient in forming acetaldehyde in the 7-300 temperature range (alpha = 1.21 x 10$^{-10}$ cm$^3$ s$^{-1}$ and beta = 0.16). On the contrary, our new computations disprove the formation of acetaldehyde through reaction (3) (alpha = 1.84, 0.67 x 10$^{-13}$ cm$^3$ s$^{-1}$ and beta = -0.07, -0.95). Path (1) was showed to be inefficient too by recent computations, while path (4) was formerly considered for glycolaldehyde formation, having acetaldehyde as a by-product. In conclusions, of the four above paths only two, the (2) and (4), are potentially efficient gas-phase reaction routes for the formation of acetaldehyde and we encourage astrochemical modellers to only consider them. Comparison with astronomical observations suggest that path (4) may actually play the major role.