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首页> 外文期刊>The Journal of Chemical Physics >To kink or not: A search for long-chain cumulenones using microwave spectral taxonomy
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To kink or not: A search for long-chain cumulenones using microwave spectral taxonomy

机译：扭结或否：使用微波光谱分类进行搜索长链Cumulenones

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A systematic search for carbon-chain cumulenones beyond H2C4O has been undertaken using microwave spectral taxonomy in combination with a pulsed jet discharge source. No evidence was found for the C-2 upsilon isomer of H2C5O or its longer derivatives, but HC(O)C4H, the longer variant of propynal, HC(O)CCH, was identified instead. Its rotational and leading centrifugal distortion constants have been derived to high accuracy from detection of both a- and b-type lines; those below 40 GHz were measured using a Fabry-Perot cavity, while lines between 40 and 72 GHz were recorded by double resonance techniques. Overwhelming evidence for the identification is provided by detection of HC(O)C4D, DC(O)C4H, and HC(O-18)C4H at the expected frequencies using isotopically enriched samples. Because HC(O-18)C4H is produced with comparable abundance when using either O-18(2) or (CO)-O-18 as the source of oxygen, and because (HC)-C-13(O)C4H is not preferentially formed when starting from (CO)-C-13, atomic oxygen appears to be a key reactant in formation, plausibly via O insertion, e.g., H2CC2n+2H + O -> HC(O)C2n+2H + H. Under the same experimental conditions, HC(O)CCH is more than 10 times more abundant than H2C3O, regardless of the source of oxygen, and no evidence is found for cyclopropenone, c-C3H2O. Taken together, these observations indicate that propynal and longer chains with an odd number of carbon atoms are either energetically more stable than cumulenones of the same size, are kinetically favored products, or both. On the basis of the HC(O)C4H discovery, searches for the isovalent sulfur species, HC(S)C4H, and HC(O)C6H have been conducted. Guided by new quantum chemical calculations, the rotational spectra of both were observed in the centimeter-wave band with the same spectrometer. Published by AIP Publishing.
机译：已经使用微波光谱分类法与脉冲喷射放电源组合使用微波光谱分类物进行了超出H2C4O之外的碳链Cumulenones的系统搜索。没有发现H2C5O的C-2 Upsilon异构体或其较长的衍生物的证据，但是HC（O）C4h，鉴定了propynal，HC（O）CCH的较长变体。它的旋转和前导的离心畸变常数已经从检测到A-和B型线路中获得高精度;使用法布里 - 珀罗腔测量低于40GHz的那些，而Double Assonance技术记录了40至72GHz之间的线。通过在使用同位素富集的样品的预期频率下检测HC（O）C4D，DC（O）C4H和HC（O-18）C4H的HC（O）C4D，DC（O）C4H和HC（O-18）C4H来提供压倒性的证据。因为当使用O-18（2）或（CO）-O-18作为氧气来源时，用可比丰度产生HC（O-18）C4H，并且因为（HC）-C-13（O）C4H是从（CO）-C-13开始时不优先形成，原子氧似乎是形成的关键反应物，可编合的通过O插入，例如H 2CC2N + 2H + O-> HC（O）C2N + 2H + H.无论氧气源，HC（O）CCH的实验条件相同的实验条件，HC（O）CCH比H2C3O多10倍，并且没有发现环丙酮，C-C3H2O的证据。在一起，这些观察结果表明，具有奇数碳原子的ProPynal和更长的链比相同尺寸的增荷碱能量更稳定，是重要的产品，或两者。在HC（O）C4H发现的基础上，已经进行了对等价硫种类，HC（S）C4h和HC（O）C6H的搜索。通过新的量子化学计算引导，在具有相同光谱仪的厘米波带中观察到两者的旋转光谱。通过AIP发布发布。

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