Dicarbon defect in hexagonal boron nitride monolayer - a theoretical study

IF 1.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
T. Korona, J. Jankowska, Emran Masoumifeshani
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引用次数: 1

Abstract

A comprehensive theoretical study of the lowest electronic vertical excitations of the CBCN defect in the monolayer of hexagonal boron nitride has been performed. Both the periodic boundary conditions approach and the finite-cluster simulation of the defect have been utilized at the density-functional theory (DFT) level. Clusters of increasing sizes have been used in order to estimate artefacts resulting from edge effects. The stability of the results with respect to several density functionals and various basis sets has been also examined. High-level ab initio calculations with methods like EOM-CCSD, ADC(2), and TD-CC2, were performed for the smallest clusters. It turns out that TD-DFT with the CAM-B3LYP functional gives similar lowest excitation energies as EOM-CCSD, ADC(2), and TD-CC2. The lowest excitation energies resulting from the periodic-boundary calculation utilizing the Bethe-Salpeter equation are in agreement with the results for finite clusters. The analysis of important configurations and transition densities shows that for all studied methods, the lowest excited state is localized on two carbon atoms and their closest neighbours and has a large dipole transition moment. The optimized geometries for the lowest two excited states indicate that in both cases the carbon-carbon bond becomes a single bond, while for the second excited state additionally one from boron-nitrogen bonds looses its partially double character. The calculation of the excitation energies at the respective optimal geometry reveals that these two energies become about 0.5 eV lower than vertical excitations from the ground-state geometry.
六方氮化硼单层碳缺陷的理论研究
本文对六方氮化硼单层中CBCN缺陷的最低电子垂直激发进行了全面的理论研究。在密度泛函理论(DFT)水平上,利用周期边界条件方法和有限簇模拟缺陷。为了估计由边缘效应产生的伪影,已经使用了尺寸不断增加的簇。本文还检验了结果对几种密度泛函和各种基集的稳定性。使用EOM-CCSD、ADC(2)和TD-CC2等方法对最小的簇进行高级从头计算。结果表明,具有CAM-B3LYP泛函的TD-DFT具有与EOM-CCSD、ADC(2)和TD-CC2相似的最低激发能。利用Bethe-Salpeter方程的周期性边界计算得到的最低激发能与有限簇的结果一致。对重要构型和跃迁密度的分析表明,在所有研究方法中,最低激发态都定位于两个碳原子及其最近邻,并且具有较大的偶极子跃迁矩。最低两个激发态的优化几何结构表明,在这两种情况下,碳碳键都变成了单键,而在第二激发态中,硼氮键失去了部分双键特征。在各自最优几何形状下的激发能计算表明,这两个能量比基态几何形状的垂直激发低约0.5 eV。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Canadian Journal of Chemistry
Canadian Journal of Chemistry 化学-化学综合
CiteScore
1.90
自引率
9.10%
发文量
99
审稿时长
1 months
期刊介绍: Published since 1929, the Canadian Journal of Chemistry reports current research findings in all branches of chemistry. It includes the traditional areas of analytical, inorganic, organic, and physical-theoretical chemistry and newer interdisciplinary areas such as materials science, spectroscopy, chemical physics, and biological, medicinal and environmental chemistry. Articles describing original research are welcomed.
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