Vibronic interactions proceeding from combined analytical and numerical considerations: Covalent functionalization of graphene by benzene, distortions, electronic transitions

Abstract

Chemically bound states of benzene molecules with graphene are studied both analytically and numerically. The states are formed by switching off intrabonds of π-electrons in C6 rings to interbonds. A number of different undistorted and distorted structures are established both with aligned and with transversal mutual orientation of benzene and graphene. The vibronic interactions causing distortions of bound states are found, by using a combination of analytical and numerical considerations. This allows one to determine all electronic transitions of π-electrons without explicit numerical calculations of excited states, to find the conical intersections of potentials, and to show that the mechanism of distortions is the pseudo-Jahn-Teller effect. It is found that the aligned distorted benzene molecule placed between two graphene sheets makes a chemical bond with both of them, which may be used for fastening of graphene sheets together.

CO2 and CH2 Adsorption on Copper-Decorated Graphene: Predictions from First Principle Calculations

“…Composites and hybrid structures, as well as nanoobjects based on graphene, has attracted huge attention in experimental and theoretical studies during the last decade [16][17][18][19][20][21][22] after this material was discovered in 2004 by Novoselov and Geim [23]. The decoration of graphene with metals (e.g., Fe [24], Pt [25,26], Pd [27]), as well as organic (e.g., tetracyanoethylene [28]) and inorganic compounds (e.g., Bi 2 O 3 [29]), could improve electrocatalytic adsorption and gas sensing properties toward different gases Different graphene-based catalysts for direct electrochemical CO 2 reduction were reported in the literature, e.g., atomic Fe dispersed on nitrogen-doped graphene [30], Bdoped graphene [31], N-doped graphene [32], defective graphene produced by a nitrogen removal procedure from N-doped graphene [33], Ni-decorated graphene [34], Co 3 O 4 spinel nanocubes on N-doped graphene [35], etc.…”