Scelta Demetrio, Ceppatelli Matteo, Bini Roberto, Pakhomova Anna, Garbarino Gaston, Mezouar Mohamed, Santoro Mario
European Laboratory for Nonlinear Spectroscopy, LENS, Via Nello Carrara 1, 50019 Sesto Fiorentino (FI), Italy.
Consiglio Nazionale delle Ricerche-Istituto di Chimica dei Composti OrganoMetallici, CNR-ICCOM, Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy.
J Chem Phys. 2023 Aug 28;159(8). doi: 10.1063/5.0157907.
While polymeric carbon monoxide (pCO) has been experimentally found to remain amorphous and undecomposed at room temperature up to 50 GPa, the question of whether crystalline counterparts of it can be obtained naturally raises. From different computational studies, it can be inferred that either the crystallization of amorphous pCO (a-pCO) or its decomposition into a mixture of CxOy suboxides (x > y) or carbon and CO2 may occur. In this study, we report experimental investigations of the high temperature (700-4000 K) transformation of a-pCO in the 47-120 GPa pressure range, conducted by x-ray diffraction in laser heated diamond anvil cells. Our results show the formation of no crystalline phases other than CO2 phase V, thus indicating the decomposition of the pristine a-pCO into CO2 and, likely, a mixture of amorphous CxOy suboxides and amorphous carbon hardly detectable at extreme conditions. These results support the theoretical picture of the pCO decomposition. We also show that the pressure-temperature kinetic border for this decomposition is very steep, thus indicating a strongly pressure-dependent kinetic barrier.
虽然实验发现聚合一氧化碳(pCO)在室温下至50吉帕斯卡时保持非晶态且不分解,但它是否能自然形成晶体对应物的问题随之而来。从不同的计算研究可以推断,非晶态pCO(a-pCO)要么结晶,要么分解成CxOy低价氧化物(x > y)或碳与二氧化碳的混合物。在本研究中,我们报告了在47 - 120吉帕斯卡压力范围内对a-pCO在高温(700 - 4000 K)下转变的实验研究,该研究通过激光加热金刚石对顶砧细胞中的x射线衍射进行。我们的结果表明,除了二氧化碳的V相外,没有形成其他晶相,这表明原始的a-pCO分解成了二氧化碳,并且可能分解成了在极端条件下难以检测到的非晶态CxOy低价氧化物和非晶态碳的混合物。这些结果支持了pCO分解的理论图景。我们还表明,这种分解的压力-温度动力学边界非常陡峭,这表明动力学势垒强烈依赖于压力。