Wilson Jake, Faginas-Lago Noelia, Vekeman Jelle, Cuesta Inmaculada G, Sánchez-Marín José, Sánchez de Merás Alfredo
Instituto de Ciencia Molecular, Universitat de València, Catedràtic José Beltrán 2, 46980, Paterna, Spain.
Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Consortium for Computational Molecular and Materials Sciences (CMS)2, Via Elce di Sotto 8, 06123, Perugia, Italy.
Chemphyschem. 2018 Mar 19;19(6):774-783. doi: 10.1002/cphc.201701387. Epub 2018 Feb 13.
The interaction of CO with graphene was studied at different theoretical levels. Quantum-mechanical calculations on finite graphene models with the use of coronene for coupled cluster calculations and circumcoronene for B97D calculations showed that there was no preferential site for adsorption and that the most important factor was the orientation of CO relative to graphene. The parallel orientation was preferred, with binding energies around 9 kJ mol at the CCSD(T) and B97D levels, which was in good agreement with experimental findings. From a large number of CO-circumcoronene and CO-CO interactions, computed at different distances and randomly generated orientations, parameters were fit to the improved Lennard-Jones potential. Such potentials, together with others describing the intramolecular dynamics of graphene, were subsequently employed in classical molecular-dynamics simulations of the adsorption of CO on graphene by using the canonical ensemble. The obtained results showed that the introduction of flexibility in graphene, which simulated the effects associated to curvature of the surface, diminished the adsorption level and that, as expected, adsorption also diminished with temperature.
在不同理论水平下研究了一氧化碳与石墨烯的相互作用。使用并五苯进行耦合簇计算以及使用外接并五苯进行B97D计算，对有限石墨烯模型进行量子力学计算，结果表明不存在优先吸附位点，最重要的因素是一氧化碳相对于石墨烯的取向。平行取向更受青睐，在CCSD(T)和B97D水平下结合能约为9 kJ mol，这与实验结果吻合良好。通过在不同距离和随机生成的取向下计算大量一氧化碳-外接并五苯和一氧化碳-一氧化碳相互作用，将参数拟合到改进的 Lennard-Jones 势。随后，利用正则系综，将此类势与其他描述石墨烯分子内动力学的势一起用于一氧化碳在石墨烯上吸附的经典分子动力学模拟。所得结果表明，引入模拟与表面曲率相关效应的石墨烯柔韧性会降低吸附水平，并且正如预期的那样，吸附也会随温度降低。
