A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

Topological Data Analysis (TDA) is a powerful mathematical theory, largely unexplored in theoretical chemistry. In this work we demonstrate how TDA provides new insights into topological features of electron densities and reduced density gradients, by investigating the effects of relativity on the bonding of the Au₄-S-C₆H₄-S′-Au′₄ molecule. Whereas recent analyses of this species carried out with the Quantum Theory of Atoms-In-Molecules (a previous study) concluded, from the emergence of new topological features in the electron density, that relativistic effects yielded noncovalent interactions between gold and hydrogen atoms, we show from their low persistence values (which decrease with increased basis set size) these features are not significant. Further analysis of the reduced density gradient confirms no relativity-induced noncovalent interactions in Au₄-S-C₆H₄-S′-Au′₄. We argue TDA should be integrated into electronic structure analysis methods, and be considered as a basis for the development of new topology-based approaches.     

Directionality of Halogen Bonds: An Interacting Quantum Atoms (IQA) and Relative Energy Gradient (REG) Study

Interacting Quantum Atoms (IQA) and Interacting Quantum Fragments (IQF) analyses are used to study (X=Cl and Br) model complexes in order to determine the origin of halogen bond directionality. IQA allows for the calculation of intra- and interatomic classical and exchange-correlation energies, which can be used to determine the energetic nature of the changes that occur when deviating from the preferred halogen bond approach. The Relative Energy Gradient (REG) method is also applied to rank the IQA energies and reveal which energy contributions best describe the total behavior of the system. Indeed, all the pairwise interactions and atomic self-energies are angularly dependent; some terms favor the linear structure and some tend toward nonlinear arrangements. For instance, when the C−X−N angle is altered, the halogen-nitrogen interaction energy behaves like the total energy of the system while the carbon-nitrogen interaction works against the total energy profile. Furthermore, the REG values reveal that the contribution of the halogen-nitrogen interaction to the total behavior of the system is small. Instead, the secondary interactions (e. g., fluorine-nitrogen and carbon-hydrogen interactions) and atomic self-energies are mainly responsible for the angular preference of these halogen bonds. Finally, IQF calculations followed by REG analysis reveal the importance of the self-energy of the fragments.     

Borotropy: The Mechanism of Boron Transfer Between Adjacent N-Atoms of Pyrazol-1-yl Rings

This work examines theoretically the problem of the migration of borane groups between the nitrogen atoms of pyrazolyl rings. We have studied as a model the BH₂ pyrazol-1-yl derivatives to determine the effects of substituents on the pyrazole ring; also 1-(9-borabicyclo[3.3.1]nonan-9-yl)-1H-pyrazoles to compare the calculated barriers with the experimental ones as well as to determine steric effects, i. e., how the buttressing effect increases the rate. The interacting quantum atoms methodology has been used for partitioning the energy of the systems in their stationary points into the contribution of pyrazole and BH₂ group and their mutual interaction.     

On the Addition of Aryl Radicals to Graphene: The Importance of Nonbonded Interactions

Dispersion‐corrected density functional theory is utilized to study the addition of aryl radicals to perfect and defective graphene. Although the perfect sheet shows a low reactivity against aryl diazonium salts, the agglomeration of these groups and the addition onto defect sites improves the feasibility of the reaction by increasing binding energies per aryl group up to 27 kcal mol^?1. It is found that if a single phenyl radical interacts with graphene, the covalent and noncovalent additions have similar binding energies, but in the particular case of the nitrophenyl group, the adsorption is stronger than the chemisorption. The single vacancy shows the largest reactivity, increasing the binding energy per aryl group by about 80 kcal mol^?1. The zigzag edge ranks second, enhancing the reactivity 5.4 times with respect to the perfect sheet. The less reactive defect site is the Stone–Wales type, but even in this case the addition of an isolated aryl radical is exergonic. The arylation process is favored if the groups are attached nearby and on different sublattices. This is particularly true for the ortho and para positions. However, the enhancement of the binding energies decreases quickly if the distance between the two aryl radicals is increased, thereby making the addition on the perfect sheet difficult. A bandgap of 1–2 eV can be opened on functionalization of the graphene sheets with aryl radicals, but for certain configurations the sheet can maintain its semimetallic character even if there is one aryl radical per eight carbon atoms. At the highest level of functionalization achieved, that is, one aryl group per five carbon atoms, the bandgap is 1.9 eV. Regarding the effect of using aryl groups with different substituents, it is found that they all induce the same bandgap and thus the presence of NO₂, H, or Br is not relevant for the alteration of the electronic properties. Finally, it is observed that the presence of tetrafluoroborate can induce metallic character in graphene.     

Thermo-physical and stability properties of raw and functionalization of graphene nanoplatelets-based aqueous nanofluids

This research aimed to evaluate the thermal viscosity, stability, conductivity and density of coolants including PEG-functionalized graphene nanoplatelets (GNPs) and gum Arabic (GA)-treated GNPs as a base fluid at various temperatures and concentrations. The present study explores the impacts of GNPs functionalized with poly ethylene glycol (PEG) on the colloidal stability and thermophysical properties of water-based PEG-functionalized GNPs suspensions as a new generation of heat transfer fluids. To this end, PEG-functionalized GNPs as a covalent sample and GA-treated GNPs were synthesized and their colloidal stabilities were traced via UV–vis spectrometry. After functionalized, colloidal stability results indicate less sedimentation for covalent samples (less than 10%) that that of noncovalent one (almost 20%) after a 15-day period. In addition, all the thermophysical properties e.g. thermal conductivity, density and viscosity were measured experimentally. Further, it has shown that by loading PEG-functionalized GNPs in the water, the increasing rate of the density and viscosity is not significant, while water-based GA-treated GNPs nanofluids showed higher rates of increase. Interestingly, the water-based PEG-functionalized GNP nanofluids at very low concentration significantly increase the thermal conductivity in comparison with that of non-covalent nanofluid at the same concentration and temperature and defiantly water.     

On the Relationship between Hydrogen Bond Strength and the Formation Energy in Resonance-Assisted Hydrogen Bonds

Resonance-assisted hydrogen bonds (RAHB) are intramolecular contacts that are characterised by being particularly energetic. This fact is often attributed to the delocalisation of π electrons in the system. In the present article, we assess this thesis via the examination of the effect of electron-withdrawing and electron-donating groups, namely −F, −Cl, −Br, −CF₃, −N(CH₃)₂, −OCH₃, −NHCOCH₃ on the strength of the RAHB in malondialdehyde by using the Quantum Theory of Atoms in Molecules (QTAIM) and the Interacting Quantum Atoms (IQA) analyses. We show that the influence of the investigated substituents on the strength of the investigated RAHBs depends largely on its position within the π skeleton. We also examine the relationship between the formation energy of the RAHB and the hydrogen bond interaction energy as defined by the IQA method of wave function analysis. We demonstrate that these substituents can have different effects on the formation and interaction energies, casting doubts regarding the use of different parameters as indicators of the RAHB formation energies. Finally, we also demonstrate how the energy density can offer an estimation of the IQA interaction energy, and therefore of the HB strength, at a reduced computational cost for these important interactions. We expected that the results reported herein will provide a valuable understanding in the assessment of the energetics of RAHB and other intramolecular interactions.     

Cooperativity and Anticooperativity in Ion-Water Interactions: Implications for the Aqueous Solvation of Ions

Non-additive effects in hydrogen bonds (HB) take place as a consequence of electronic charge transfers. Therefore, it is natural to expect cooperativity and anticooperativity in ion-water interactions. Nevertheless, investigations on this matter are scarce. This paper addresses the interactions of (i) the cations Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ together with (ii) the anions F⁻, Cl⁻, Br⁻, NO₃⁻ and SO₄²⁻ with water clusters (H₂O)_n, n=1–8, and the effects of these ions on the HBs within the complete molecular adducts. We used quantum chemical topology tools, specifically the quantum theory of atoms in molecules and the interacting quantum atoms energy partition to investigate non-additive effects among the interactions studied herein. Our results show a decrease on the interaction energy between ions and the first neighbouring water molecules with an increment of the coordination number. We also found strong cooperative effects in the interplay between HBs and ion-dipole interactions within the studied systems. Such cooperativity affects considerably the interactions among ions with their first and second solvation shells in aqueous environments. Overall, we believe this article provides valuable information about how ion-dipole contacts interact with each other and how they relate to other interactions, such as HBs, in the framework of non-additive effects in aqueous media.     

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H₂O)₂. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built.     

When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms

Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra‐atomic and inter‐atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra‐atomic and inter‐atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange‐correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange‐correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc.     

Chemical Functionalisation and Photoluminescence of Graphene Quantum Dots

Chemical modification of graphene quantum dots (GQDs) can influence their physical and chemical properties; hence, the investigation of the effect of organic functional groups on GQDs is of importance for developing GQD–organic hybrid materials. Three peripherally functionalised GQDs having a third‐generation dendritic wedge (GQD‐ 2 ), long alkyl chains (GQD‐ 3 ) and a polyhedral oligomeric silsesquioxane group (GQD‐ 4 ) were prepared by the Cu^I‐catalysed Huisgen cycloaddition reaction of GQD‐ 1 with organic azides. Cyclic voltammetry indicated that reduction occurred on the surfaces of GQD‐ 1 – 4 and on the five‐membered imide rings at the periphery, and this suggested that the functional groups distort the periphery by steric interactions between neighbouring functional groups. The HOMO–LUMO bandgaps of GQD‐ 1 – 4 were estimated to be approximately 2 eV, and their low‐lying LUMO levels (<?3.9 eV) were lower than that of phenyl‐C₆₁‐butyric acid methyl ester, an n‐type organic semiconductor. The solubility of GQD‐ 1 – 4 in organic solvents depends on the functional groups present. The functional groups likely cover the surfaces and periphery of the GQDs, and thus increase their affinity for solvent and avoid precipitation. Similar to GQD‐ 2 , both GQD‐ 3 and GQD‐ 4 emitted white light upon excitation at 360 nm. Size‐exclusion chromatography demonstrated that white‐light emission originates from the coexistence of differently sized GQDs that have different photoluminescence emission wavelengths.     

Chemical bonding in excited states: Energy transfer and charge redistribution from a real space perspective

This work provides a novel interpretation of elementary processes of photophysical relevance from the standpoint of the electron density using simple model reactions. These include excited states of H₂ taken as a prototype for a covalent bond, excimer formation of He₂ to analyze non‐covalent interactions, charge transfer by an avoided crossing of electronic states in LiF and conical interesections involved in the intramolecular scrambling in C₂H₄. The changes of the atomic and interaction energy components along the potential energy profiles are described by the interacting quantum atoms approach and the quantum theory of atoms in molecules. Additionally, the topological analysis of one‐ and two‐electron density functions is used to explore basic reaction mechanisms involving excited and degenerate states in connection with the virial theorem. This real space approach allows to describe these processes in a unified way, showing its versatility and utility in the study of chemical systems in excited states. © 2017 Wiley Periodicals, Inc.     

Electrostatic calculation of the substituent effect: an efficient test on isolated molecules

The energy of a disubstituted molecule has often been approximated by simple electrostatic formulas that represent the substituents as poles or dipoles. Herein, we test this approach on a new model system that is more direct and more efficient than testing on acid-base properties. The energies of 27 1,4-derivatives of bicyclo[2.2.2]octane were calculated within the framework of the density functional theory at the B3LYP/6-311+G(d,p) level; interaction of the two substituents was evaluated in terms of isodesmic homodesmotic reactions. This interaction energy, checked previously on some experimental gas-phase acidities, was considered to be accurate and served as reference to test the electrostatic approximation. This approximation works well in the qualitative sense as far as the sign and the order of magnitude are concerned: beginning with the strongest interaction between two poles, a weaker interaction between pole and dipole, and the weakest between two dipoles. However, all the electrostatic calculations yield energies that are too small, particularly for weak interaction, and this fundamental defect is not remedied by some possible improvements. In particular, variation of the effective permittivity would require a physically impossible value less than unity. The explanation must lie in a more complex distribution of electron density than anticipated in the electrostatic model. It also follows that possible conclusions about the transmission of substituent effects "through space" have little validity.     

Chain-growth polycondensation via the substituent effect: Investigation in to the role of initiator and base on the synthesis of poly(N-octyl benzamide)

A detailed investigation into the role of initiator structure, the presence of an initiator, and basicity of the non-nucleophilic base in the chain-growth condensation (CGC) synthesis of poly(N-octyl benzamide) was conducted. A series of phenyl ester dimethyl amide initiators with different leaving groups were synthesized and used in the CGC preparation of poly(N-octyl benzamide). Additional polymerizations were conducted without the presence of an initiator and with different non-nucleophilic bases. Kinetic studies, along with nuclear magnetic resonance spectroscopy and gel-permeation chromatography, were used to determine progress of the reaction, molecular weights, and molecular weight distributions. The experimental and computational results demonstrated that initiators containing electron-withdrawing substituent phenyl esters, such as the p-nitrophenyl ester, and electron-withdrawing carbonyl character on the parent benzoate produce polymers with controllable molecular weights and narrow molecular weight distributions. Whereas, initiating species that contain electron-donating character on the benzoate backbone, such as dimethylamino and methyl ester groups, produce polymers that resemble the results from reactions involving no initiators at all, indicating poor polymerization control.     

On the strength of hydrogen bonding within water clusters on the coordination limit

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster. We could expand our previously reported hierarchy of HB strength in these systems (Phys. Chem. Chem. Phys., 2016, 18 , 19557) to include tetracoordinated monomers. Surprisingly, the HBs between tetracoordinated water molecules are not the strongest HBs despite the widespread occurrence of these motifs (e.g., in ice I_h). The strongest HBs within H₂O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because (a) it reduces HB anticooperativity associated with double HB donors and acceptors and (b) it results in a larger number of favorable interactions in the system. Finally, we also discuss (a) the importance of exchange-correlation to discriminate among the different examined types of HBs within H₂O clusters, (b) the use of the above-mentioned scale to quickly assess the relative stability of different isomers of a given water cluster, and (c) how the findings of this research can be exploited to indagate about the formation of polymorphs in crystallography. Overall, we expect that this investigation will provide valuable insights into the subtle interplay of tri- and tetracoordination in HB donors and acceptors as well as the ensuing interaction energies within H₂O clusters.     

Recent advances in covalent functionalization of carbon nanomaterials with polymers: Strategies and perspectives

Carbon nanomaterials (CNMs) have been proposed as promising nanofillers for polymer composites because of their high surface area, structural flexibility, good mechanical strength, and their unique thermal, optical, and electronic properties. However, the strong van der Waals interactions between individual nanoparticles have limited the manipulation of CNMs and restricted their use in many promising fields. The functionalization of CNMs has attracted great interest on synthesis of complex structures, and helped establish different facile, scalable, controllable and low-cost methods to graft well-defined polymers onto the surfaces of CNMs. This review highlights the advances made in recent years on the functionalization chemistry of carbon nanotubes and graphene with polymers by both the “grafting from” and “grafting to” techniques. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 622–631     

Enhancement of electro-optical response of ferroelectric liquid crystal: the role of graphene quantum dots

We present a pioneer study depicting a significant improvement in the photoluminescence (PL) intensity and display of an expeditious electro-optic response of ferroelectric liquid crystal (FLC) when doped with graphene quantum dots (GQDs). Significant threefold enhancement in PL intensity of GQDs/FLC composite material can be ascribed to the additive combination of emissions from GQDs and FLCs. Furthermore, promptness in electro-optical response by a factor of 34% can be attributed to the lowering of rotational viscosity of the FLC material due to the incorporation of GQDs. These results would certainly be helpful in realisation of highly luminescent and faster generation of LC systems.     

The effects of higher orders of perturbation theory on the correlation energy of atoms and bonds in molecules

We examine, for the first time, the effects of higher orders of Møller–Plesset perturbation theory on the individual atoms within a molecule and the bonds between them, via the topological energy partitioning method of interacting quantum atoms. In real terms (i.e., not by absolute value) MP3 decreases the correlation energy of a bond, and MP4SDQ also decreases the energy of the atoms at either end of the bond. In addition, we investigated long‐range through‐space dispersive effects on a H₂ oligomer. Overall, MP3 is the largest correction to the correlation energy, and most of that energy is allocated to chemical bonds, reducing their values in actual terms. The MP4SDQ bond correlation correction, despite being relatively small, tends to have two effects: (i) for small or negative correlation energies MP4SDQ tends to decrease the bond correlation values even more, and (ii) for large (positive) bond correlation energies MP4SDQ tends to restore the bond correlation energies from the MP3 back toward the MP2 values. Furthermore, each individual part of a molecule or complex (atom or bond) has a specific convergence pattern for the MPn series: through‐space interactions converge at MP2 but bonds converge at MP3 level. The atomic correlation energy appears to head toward convergence at the MP4 level.