The influence of distribution of hydroxyl groups on vibrational spectra of fullerenol C60(OH)24 isomers: DFT study

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Highlights

  • The broadening of O–H stretching vibration band corresponds to close packing of hydroxyl group over C60 surface.

  • The calculations at B3LYP/6-31G(d,p) level of theory are in good agreement with the experimental data.

  • The O–H vibrational modes can potentially serve as an estimator of hydroxyl group distribution over C60 surface.

  • The C–C Raman stretching vibration in hexagons of C60(OH)24 molecule can be potential sensor the molecule structure.

Abstract

The infrared and Raman spectra of C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been investigated using first principle DFT calculations at the B3LYP/6-31G(d,p) level of theory. The important features of the obtained geometries have been measured and compared to experimental results. The reference calculations of C60 molecule geometry and vibrational spectra have been made and compared to available experimental data. The striking differences of infrared spectra between C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been shown and discussed. The OH modes have been identified as the most sensitive to C60(OH)24 isomer configuration. The C–C stretching modes in the Raman spectra of the C60(OH)24 molecule have been found as a potential sensor of OH groups distribution over fullerene C60 surface.

Introduction

Since the discovery of the C60 buckminsterfullerene [1] there are a lot of experimental [2], [3] and theoretical [4], [5], [6], [7], [8] papers about the dynamics and structure of this molecule. In the recent years the water-soluble fullerenes derivatives are of great interest, because of their potential medical applications. One of the most promising fullerenes derivatives is polyhydroxylated fullerene, called fullerenol or fullerol. Both in vitro and in vivo studies have shown that C60(OH)n, (n = 1–36), can be a potential antioxidative agents and free radical scavengers in biological systems [9], [10], [11], [12]. One of the experimental study carried out by Mirkov et al. shows that the C60(OH)24 fullerenol is able to reduce nitric oxide in mammals body [13]. The potential physical scavenging properties of fullerenols were also investigated by the molecular dynamics simulations [14], [15]. The physisorption of NO by single C60(OH)24 molecule has been estimated. Another important potential medical application, caused by cytotoxicity of fullerenols is cancer therapeutics [16], [17], [18], [19]. Besides medical applications, the fullerenol related materials can be potentially used as molecular optical devices [20], [21], [22]. There are some reports about the methods of synthesizing fullerenols in laboratory [23], [24]. The identification of OH groups distribution over C60 surface is very important in the view of its interaction with water. The high concentration of OH groups in biological systems leads to mainly hydrogen bonding interactions [25]. Although, the recent mass-spectroscopy study proves their ability to estimate the number of the hydroxyl groups attached to the C60 sphere [26], [27], the distribution of this groups is still unknown. The promising approach may be the first principle computer simulations. The structure stability of different isomers of isolated C60(OH)24 molecule has been investigated already by all electron DFT calculations [28]. The most stable structure was recognized as an OH ring around the fullerene equator. In this study we would like to present infrared (IR) and Raman spectra of two C60(OH)24 isomers of uniform and non-uniform distribution of OH groups calculated with the use of DFT method. We compare the results and discuss the differences in vibrational spectra between different isomers of C60(OH)24 molecule. We have also calculated IR and Raman spectra for C60 fullerene as a reference.

Section snippets

Computational methods

The PM3 Hamiltonian [29], which is well-known to provide a good results for hydrogen bonding systems, was used as a preliminary optimization method of C60 molecule (Fig. 1a) and C60(OH)24 isomers (Fig. 1b and c) structures. Obtained geometries have been further optimized using density functional theory (DFT) method. For this purpose, we have used hybrid B3LYP expression for the exchange–correlation potential together with the 6-31G(d,p) basis set to solve Kohn–Sham equations [30]. Chosen basis

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