Issue 11, 2013
From the journal:

Physical Chemistry Chemical Physics

Quantum chemical investigation of epoxide and ether groups in graphene oxide and their vibrational spectra†

Alister J. Page,a   Chien-Pin Chou,b   Buu Q. Pham,c   Henryk A. Witek,b   Stephan Irle*d  and  Keiji Morokuma*ae  

* Corresponding authors

a Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
E-mail: keiji.morokuma@emory.edu

b Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan

c Institute for Computational Science and Technology, Vietnam National University, Ho Chi Minh City, Vietnam

d Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
E-mail: sirle@chem.nagoya-u.ac.jp

e Cherry L. Emerson Centre for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322, USA

Abstract

We present a detailed analysis of the factors influencing the formation of epoxide and ether groups in graphene nanoflakes using conventional density functional theory (DFT), the density-functional tight-binding (DFTB) method, π-Hückel theory, and graph theoretical invariants. The relative thermodynamic stability associated with the chemisorption of oxygen atoms at various positions on hexagonal graphene flakes (HGFs) of D6h-symmetry is determined by two factors – viz. the disruption of the π-conjugation of the HGF and the geometrical deformation of the HGF structure. The thermodynamically most stable structure is achieved when the former factor is minimized, and the latter factor is simultaneously maximized. Infrared (IR) spectra computed using DFT and DFTB reveal a close correlation between the relative thermodynamic stabilities of the oxidized HGF structures and their IR spectral activities. The most stable oxidized structures exhibit significant IR activity between 600 and 1800 cm−1, whereas less stable oxidized structures exhibit little to no activity in this region. In contrast, Raman spectra are found to be less informative in this respect.

Graphical abstract: Quantum chemical investigation of epoxide and ether groups in graphene oxide and their vibrational spectra

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Article information

DOI
https://doi.org/10.1039/C3CP00094J
Article type
Paper
Submitted
09 Jan 2013
Accepted
16 Jan 2013
First published
16 Jan 2013

Phys. Chem. Chem. Phys., 2013,15, 3725-3735

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Quantum chemical investigation of epoxide and ether groups in graphene oxide and their vibrational spectra

A. J. Page, C. Chou, B. Q. Pham, H. A. Witek, S. Irle and K. Morokuma, Phys. Chem. Chem. Phys., 2013, 15, 3725 DOI: 10.1039/C3CP00094J

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