On the role of substituent in noncovalent functionalization of graphene and organophosphor recognition: IQA and SAPT perspective

Abstract

Despite importance of integrating organic molecules with graphene to fabricate graphene-based electronic devices, the role of substituents and interface stabilizing forces are poorly understood. In this work, the interactions of 7,7,8,2,3,5,7,8,, hydroquinone (Q), and tetrafluorohydroquinone (TFQ) with graphene have been investigated by means of interacting quantum atoms and SAPT(DFT). In addition, in context of potential design of a graphene-based sensor for detection of the nerve agent sarin, we studied the interaction of graphene and the organic molecules with the dimethyl methylphosphonate (DMMP)-the molecule that mimics sarin. The results show that the organic molecules attach to graphene via C(sp 2 )Á Á ÁC(sp 2 ), C(sp 2 )Á Á ÁC (sp) and HÁ Á Áp bonds. In addition, they trap DMMP via various linkages such as hydrogen, lonepairÁ Á Áp and HÁ Á Áp. The quantum effects play a significant role. The Pauli repulsion is responsible for p-doping of graphene. The substituents are stabilized on graphene by the exchange-correlation energy. The fluorination of the benzenoid ring raises the electron-sharing. The through space and through bond effects of the fluorine atoms (-F) increase the classical attraction of the cyano groups and benzenoid ring with graphene, respectively. When comparing performance of the ab initio and DFT methods, MP2 predicts too much attraction due to well-known overestimation of the dispersion energy by the uncoupled dispersion component for benzene rings, while xB97xD functional and SAPT(DFT) provide weaker interaction energies, in good agreement with each other. K E Y W O R D S graphene, interacting quantum atoms, noncovalent functionalization, SAPT, substituent effects | I N T R O D U C T I O NDue to the extraordinary properties, [1][2][3][4] graphene [5] is regarded as a promising material in various devices such as capacitors, [6][7][8] nanoelectronic devices, [9] and sensors. [10,11] Despite the superior properties of graphene, its zero band gap and its low reactivity as compared to other nanostructured carbon allotropes, [12,13] are two major obstacles for using graphene as a semiconductors or sensor. Therefore, forcing a sizable band gap and overcoming the inertness are crucial for utilization of graphene in nanoscale devices. [14][15][16] Noncovalent functionalization of graphene [16] through adsorption of organic molecules on its surface, [17] that is, surface charge transfer doping, [18][19][20][21] is a safe strategy for tuning electrical properties of graphene without damaging sp 2 carbon network of graphene. [16] Based on the nature of organic molecule adsorbed onto the graphene surface, electrons are moved to or pushed away from graphene through charge transfer (CT) interaction, [22,23] leading to tuning the electronic structure of graphene. It is parenthetically worth mentioning that it is better to consider CT interaction as a part of induction energy. [24] Regardless of the nature of adsorbates-either donor or acceptor-however, they are stabilized on the graphene surface via no...

Recent developments in symmetry‐adapted perturbation theory

“…Besides the stacked PAH dimers, understanding physisorption processes requires studying interactions between a single PAH representing the surface and a small adsorbate molecule. Using models of a graphene surface ranging in size from four (pyrene) to 14 (circumpyrene) aromatic rings, SAPT(DFT) has been used to gain insight into the adsorption of water, methane, hydrogen, Cl 2, and tetracyanoquinodimethane (TCNQ) and its derivatives . The largest calculations of this kind involve a SAPT0 analysis of the interaction between benzene (or its fluorinated derivatives) and a graphene nanoflake as large as C 150 H 30.…”

“…Using models of a graphene surface ranging in size from four (pyrene) to 14 (circumpyrene) aromatic rings, SAPT(DFT) has been used to gain insight into the adsorption of water, 200 methane, 201 hydrogen, 202 Cl 2, 203 and tetracyanoquinodimethane (TCNQ) and its derivatives. 204 The largest calculations of this kind involve a SAPT0 analysis of the interaction between benzene (or its fluorinated derivatives) and a graphene nanoflake as large as C 150 H 30. 205,206 In addition to adsorption on carbon nanostructures, interactions between small molecules and cluster models of other surfaces such as MgO, 207 TiO 2 , 208 or a metal organic framework 209 have also been subjected to the SAPT and/or SAPT(DFT) decompositions.…”

Interaction of Non‐polarizable Cations with Azaborine Isomers and Their Mono‐Substituted Derivatives: Position, Induction, and Non‐Classical Effects Matter

“…Although the SAPT partition offers an insight into the physics of the interaction between azaborines and cations, it does not provide enough information to discern the contributions of the azaborine ring and the substituent to the stabilization of the complex, neither it gives a picture of how the substituent exercises its impact: through‐bond,, (from the σ ‐ or π‐electron systems) or through‐space ( direct interaction) ,,,. One of the well‐established and robust approaches to deal with this problem is the IQA scheme, which describes the interaction energies in light of McWeeny's theory of electronic separability .…”

Interacting Quantum Atoms—A Review

“…Mitoraj and coworkers used the IQA methodology to quantify the different non-covalent interactions present in the LiN(CH ) BH and KN(CH ) BH crystals, commonly utilised as hydrogen storage materials [ 89 ]. Yourdkhani et al studied the adsorption of a series organophosphor molecules by graphene [ 90 ].…”