DFT-D Calculations Research Articles

Enhancement of gas sensing by doping of transition metal in two-dimensional As2C3 nanosheet: A density functional theory investigation

We have been motivated to explore the quest for an appropriate 2D material with the potential to capture toxic nitrogen-containing gasses (NH3, NO2, and NO). We have calculated the structural, electronic, and adsorption properties of 2D As2C3 nanosheets. The density functional theory (DFT) calculations show that NO2 and NH3 are weakly binding with the pristine As2C3 nanosheet, which restricts the use of the latter as effective sensing materials. At the same time, the NO molecule reveals better adsorption property and a significant amount of charge transfer of 0.30 e. However, the adsorption energies are significantly enhanced by introducing the doping of transition metal elements (Cu, Pd, and Pt) into the As2C3 nanosheet. Our dispersion-corrected DFT-D3 calculations found that Cu, Pd, and Pt dopants in As2C3 nanosheet not only improve the adsorption property but also significantly moderate the electronic properties, charge transfer, and work function, etc. A Bader charge transfer mechanism suggests that the amount of charge transfer from nanosheet to the NCGs and vice-versa is responsible for enhancing the sensing characteristics. Our theoretical results reveal that 0.90% doping of TM elements in As2C3 nanosheet makes it a suitable and efficient sensing device to detect the toxic pollutant gases.

Hydration mechanisms of smithsonite from DFT-D calculations and MD simulations

Investigation on the mineral−water interactions is crucial for understanding the subsequent interfacial reactions. Currently, the hydration mechanisms of smithsonite are still obscure. In this paper, the adsorption of H 2 O at different coverage rates on smithsonite (1 0 1) surface was innovatively investigated using density-functional theory (DFT) calculations and molecular dynamics (MD) simulations by analyzing adsorption model, interaction energy, atomic distance, density of state, electron density difference, concentration profile, radial distribution function and self-diffusion coefficient. We found that single H 2 O preferred to be dissociated on smithsonite (1 0 1) surface via the interaction of surface Zn with the Ow of H 2 O and H-bond between Hw of H 2 O and surface Os. However, dissociation adsorption and molecular adsorption coexisted on the smithsonite surface at a high coverage rate of H 2 O, and dissociation adsorption remained the main adsorption mechanism. Moreover, we found the interaction between smithsonite surface and H 2 O was weakened as a function of H 2 O coverage, which was because the presence of interlayer H 2 O and different layers of H 2 O decreased the reactivity of the smithsonite surface. The H 2 O is mainly adsorbed on the smithsonite surface by forming three layers of H 2 O (about 10–15 Å), with the ordering degree gradually decreasing.

Electronic and catalytic properties of Ti single atoms@SnO2 and its implications on sensing mechanism for CO

Inspired by the unprecedented catalyzing effect of single-atom catalysts, the atomically scattered Ti single-atom significantly enhancing the CO sensing performance of the SnO2(110) are investigated by using DFT-D calculations. The Ti single-atom prefers to stay on the top layer of six-fold Sn atoms. Two reaction mechanisms for CO oxidation are found on the Ti single-atom doped SnO2(110) with the moderate reaction barriers of 0.53 eV (Path I) and 0.83 eV (Path II), respectively for the rate-determining steps. The Ti single-atom doped SnO2(110) can be active and selective sensing catalyst for CO oxidation with their activation barrier (0.53 eV) is comparable with those of Pt6c/SnO2 (0.62 eV) and In-doped SnO2(110) (1.03 eV). Furthermore, the microkinetic investigation reveals that the maximum CO oxidation ratealong the Path I is 4.29 × 104s−1. This finding suggests that Ti single-atom doping can effectively improve CO oxidation at low-temperature, hence improving the SnO2 to CO sensing performance. Our study enlightens the perspective application of single-atom catalysts on gas sensing fields and provides new routes for designing new gas sensing materials.

Chameleon Behavior of a New Salt of 3-(Aminocarbonyl) Pyridinium Malonate and Implications for Polymorphism on the Salt/Cocrystal Continuum

This contribution presents a previously unreported example and comparative study of a binary crystalline adduct which exhibits a salt form in a 1:1 stoichiometry. Specifically, a new salt form of a novel 1:1 form of 3-(aminocarbonyl) pyridinium malonate is reported, and the route to isolating it from aqueous solution and the crystal chemistry of the system are characterized. Structurally, the nicotinamide dimer motif present in the polymorphic cocrystals is absent in the salt, allowing an equimolar structure arising from a singly donated proton from one malonic acid carboxylic acid group. A comparative study of the solid form landscape is presented against its known polymorphic forms I and II, which form in a 2:1 ratio of bis(nicotinamide) malonic acid, wherein computational mapping reveals the order or stability as a 1:1 salt, 2:1 cocrystal polymorph II, and 2:1 cocrystal polymorph I, the latter being the metastable form. Intriguingly, on the basis of periodic DFT-D calculations, we also propose two tentative 2:1 salt forms of cocrystal polymorph II which would be of higher stability than both the hitherto explored 2:1 cocrystalline forms and linked crystal packing/interactions with crystal growth outcomes. This study demonstrates the importance of computational studies to explore the salt/cocrystal continuum and could highlight subtle isostructural changes that could yield novel solid forms and impact physiochemical properties and morphology, providing further impetus for screening activities/characterization.

Shell-like Xenon Nano-Traps within Angular Anion-Pillared Layered Porous Materials for Boosting Xe/Kr Separation.

Adsorptive separation of xenon (Xe) and krypton (Kr) is a promising technique but remains a daunting challenge since they are atomic gases without dipole or quadruple moments. Herein we report a strategy for fabricating angular anion-pillared materials featuring shell-like Xe nano-traps, which provide a cooperative effect conferred by the pore confinement and multiple specific interactions. The perfect permanent pore channel (4-5 Å) of Ni(4-DPDS)2 MO4 (M=Cr, Mo, W) can host Xe atoms efficiently even at ultra-low concentration (400 ppm Xe), showing the second-highest selectivity of 30.2 in Ni(4-DPDS)2 WO4 and excellent Xe adsorption capacity in Ni(4-DPDS)2 CrO4 (15.0 mmol kg-1 ). Crystallography studies and DFT-D calculations revealed the energy favorable binding sites and angular anions enable the synergism between optimal pore size and polar porosity for boosting Xe affinity. Dynamic breakthrough experiments demonstrated three MOFs as efficient adsorbents for Xe/Kr separation.

Crystal structure from X-ray powder diffraction data, DFT-D calculation, Hirshfeld surface analysis, and energy frameworks of (RS)-trichlorme-thia-zide.

The structure of racemic (RS)-trichlorme-thia-zide [systematic name: (RS)-6-chloro-3-(di-chloro-meth-yl)-1,1-dioxo-3,4-di-hydro-2H-1λ6,2,4-benzo-thia-di-azine-7-sulfonamide], C8H8Cl3N3O4S2 (RS-TCMZ), a diuretic drug used in the treatment of oedema and hypertension, was determined from laboratory X-ray powder diffraction data using DASH [David et al. (2006 ▸). J. Appl. Cryst. 39, 910-915.], refined by the Rietveld method with TOPAS-Academic [Coelho (2018 ▸). J. Appl. Cryst. 51, 210-218], and optimized using DFT-D calculations. The extended structure consists of head-to-tail dimers connected by π-π inter-actions which, in turn, are connected by C-Cl⋯π inter-actions. They form chains propagating along [101], further connected by N-H⋯O hydrogen bonds to produce layers parallel to the ac plane that stack along the b-axis direction, connected by additional N-H⋯O hydrogen bonds. The Hirshfeld surface analysis indicates a major contribution of H⋯O and H⋯Cl inter-actions (32.2 and 21.7%, respectively). Energy framework calculations confirm the major contribution of electrostatic inter-actions (E elec) to the total energy (E tot). A comparison with the structure of S-TCMZ is also presented.

A structure determination protocol based on combined analysis of 3D-ED data, powder XRD data, solid-state NMR data and DFT-D calculations reveals the structure of a new polymorph of l-tyrosine.

We report the crystal structure of a new polymorph of l-tyrosine (denoted the β polymorph), prepared by crystallization from the gas phase following vacuum sublimation. Structure determination was carried out by combined analysis of three-dimensional electron diffraction (3D-ED) data and powder X-ray diffraction (XRD) data. Specifically, 3D-ED data were required for reliable unit cell determination and space group assignment, with structure solution carried out independently from both 3D-ED data and powder XRD data, using the direct-space strategy for structure solution implemented using a genetic algorithm. Structure refinement was carried out both from powder XRD data, using the Rietveld profile refinement technique, and from 3D-ED data. The final refined structure was validated both by periodic DFT-D calculations, which confirm that the structure corresponds to an energy minimum on the energy landscape, and by the fact that the values of isotropic 13C NMR chemical shifts calculated for the crystal structure using DFT-D methodology are in good agreement with the experimental high-resolution solid-state 13C NMR spectrum. Based on DFT-D calculations using the PBE0-MBD method, the β polymorph is meta-stable with respect to the previously reported crystal structure of l-tyrosine (now denoted the α polymorph). Crystal structure prediction calculations using the AIRSS approach suggest that there are three other plausible crystalline polymorphs of l-tyrosine, with higher energy than the α and β polymorphs.

Two novel 4,6-connected anion-pillared metal-organic frameworks for simultaneous separation of C3 and C4 olefins

The adsorptive separation of C3 (propane/propylene) and C4 olefins (1,3-butadiene/C4 alkenes) by a single material are of great commercial significance to make full use of these raw chemicals and adsorbents; however, the precise fabrication of porous materials with fine-tuning pores and multiple binding sites to discriminate these guest molecules remain challenging. Herein, we report two new 4,6-connected fsc-net anion-pillared copper MOFs (TIFSIX-Cu-TPB and SIFSIX-Cu-TPB) for which the cavity and functional sites can be tuned by altering the anion pillars. The unique pore structure and abundant electronegative anions, as well as aromatic rings of MFSIX-Cu-TPB (M = Ti, Si), enabled the selective discrimination of both propylene/propane (C3H6/C3H8) and 1,3-butadiene/C4 olefins, displaying high propylene (2.85 mmol g−1) and 1,3-butadiene (3.35 mmol g−1) uptake at 1 bar and 298 K. Their separation performances are confirmed by breakthrough experiments, and the adsorption sites are identified by DFT-D calculations. To the best of our knowledge, the MFSIX-Cu-TPB (M = Ti, Si) represent the first example of anion-pillared MOFs that demonstrate the high separation efficiency in C3 and C4 olefin separations.

A theoretical approach on the ability of functionalized gold nanoparticles for detection of Cd2+

Cadmium (Cd) as a toxic element that is widely present in water, soil, and air has important effects on human health, therefore proposing an accurate and selective method for detection of this element is of importance. In this article, by employing full atomistic molecular dynamics (MD) simulations and density functional theory dispersion corrected (DFT-D3) calculations, the effects of 6-mercaptonicotinic acid (MNA) and l-cysteine (CYS) on the stability of gold nanoparticles (AuNPs) and their sensitivity against Cd2+ were investigated. The obtained results indicate that pure AuNPs are not stable in water, while functionalized AuNPs with CYS and MNA groups have considerable stability without aggregation. In other words, the functional groups on the surface of AuNPs elevate their resistance against aggregation by an increase in the repulsive interactions between the gold nanoparticles. Moreover, functionalized AuNPs have considerable ability for selective detection of Cd2+ in the presence of different metal ions. Based on the MD simulation results, MNA-CYS-AuNPs (functionalized AuNPs with both functional groups) have the maximum sensitivity against Cd2+ in comparison with MNA-AuNPs and CYS-AuNPs due to the strong electrostatic interactions. DFT-D3 calculations reveal that the most probable interactions between the metal ions and functional groups are electrostatic, and Cd2+ can aggregate functionalized AuNPs due to strong electrostatic interactions with MNA and CYS groups. Moreover, charge transfer and donor–acceptor analyses show that molecular orbital interactions between the functional groups and Cd2+ can be considered as the driving force for AuNPs aggregation. A good agreement between the theoretical results and experimental data confirms the importance of the molecular modeling methods as a fast scientific protocol for designing new functionalized nanoparticles for application in different fields.

Solid-State Structural Properties of Alloxazine Determined from Powder XRD Data in Conjunction with DFT-D Calculations and Solid-State NMR Spectroscopy: Unraveling the Tautomeric Identity and Pathways for Tautomeric Interconversion.

We report the solid-state structural properties of alloxazine, a tricyclic ring system found in many biologically important molecules, with structure determination carried out directly from powder X-ray diffraction (XRD) data. As the crystal structures containing the alloxazine and isoalloxazine tautomers both give a high-quality fit to the powder XRD data in Rietveld refinement, other techniques are required to establish the tautomeric form in the solid state. In particular, high-resolution solid-state 15N NMR data support the presence of the alloxazine tautomer, based on comparison between isotropic chemical shifts in the experimental 15N NMR spectrum and the corresponding values calculated for the crystal structures containing the alloxazine and isoalloxazine tautomers. Furthermore, periodic DFT-D calculations at the PBE0-MBD level indicate that the crystal structure containing the alloxazine tautomer has significantly lower energy. We also report computational investigations of the interconversion between the tautomeric forms in the crystal structure via proton transfer along two intermolecular N–H···N hydrogen bonds; DFT-D calculations at the PBE0-MBD level indicate that the tautomeric interconversion is associated with a lower energy transition state for a mechanism involving concerted (rather than sequential) proton transfer along the two hydrogen bonds. However, based on the relative energies of the crystal structures containing the alloxazine and isoalloxazine tautomers, it is estimated that under conditions of thermal equilibrium at ambient temperature, more than 99.9% of the molecules in the crystal structure will exist as the alloxazine tautomer.

First‐principles based theoretical investigation of the adsorption of alkanethiols on the iron surface: A DFT-D3 study

The search for novel corrosion inhibitors is a never-ending and challenging task. Computational studies are fundamental to assessing the interaction of inhibitor molecules with metals, thus opening the way to design new inhibitors with specific characteristics. Herein, first-principles DFT-D3 calculations were performed to simulate the bonding of three alkanethiols, namely 11-mercaptoundecanoic acid (MDA), decanethiol (DT), hexanethiol (HT) with the iron surface Fe(110). The interaction energies obtained from different adsorption systems predicted this adsorption strength: MDA > DT > HT. The perpendicular adsorption geometries were found to be more stable than other adsorption modes. However, all adsorption configurations showed covalent interactions between sulfur atom and iron surface. Electron density difference (EDD) plots and projected density of states (PDOS) further confirmed the electron-donation and back-donation synergic interactions between interactive systems. This study showed that alkanethiols with a long carbon chain and an end-functional group had increased charge transfer and bonding with the bare iron surface, i.e., Fe(110).

Effects of defects and impurities on the adsorption of H2O on smithsonite (101) surfaces: Insight from DFT-D and MD

In this paper, DFT-D calculations and MD simulations were first performed to systematically study the H 2 O adsorption on smithsonite (101) surface with different defects and impurities, mainly including Zn-vacancy defect and Fe, Mn, Cd, Co impurities. We found the H 2 O adsorption on the defective and impurity smithsonite surfaces were all depressed compared with the perfect surface. Moreover, we found the adsorption forms of H 2 O also changed greatly. The single H 2 O on perfect surface was dissociated adsorption, which mainly included the hybridizations of Zn 3d with O 2p orbitals as well as H 1s with O 2p orbitals, while that on Zn-vacancy surfaces changed to molecular adsorption, which mainly included the hybridization between Zn 3d and O 2p orbitals, and that on impurity surfaces can be observed both molecular and dissociated adsorption, which mainly included the hybridizations of d orbital of impurity atoms with O 2p orbital as well as H 1s with O 2p orbitals for the dissociated adsorption while d orbital of impurity atoms with O 2p orbital for the molecular adsorption. The analysis results demonstrated that the adsorption of H 2 O on the perfect smithsonite (101) surface was stronger and more stable than that on the defective and impurity surfaces. The adsorption of H 2 O on defective and impurity smithsonite surfaces was all depressed than the perfect surface.

0D Bismuth(III)-Based Hybrid Ferroelectric: Tris(acetamidinium) Hexabromobismuthate(III)

Ferroelectric properties of haloantimonates(III) and halobismuthates(III) have been detected for as much as 40 structures belonging to 7 different types of anionic networks, with RMX4, R2MX5, R3M2X9, and R5M2X11 stoichiometries being the most frequently reported to host these properties. We report on the first ferroelectric of the halobismuthate(III) family with a R3MX6 stoichiometry, that is, tris(acetamidinium)hexabromobismuthate(III), (CH3C(NH2)2)3[BiBr6] (ABB), characterized by a one-component organic network. While the stoichiometry and crystal packing of ABB might seem uncomplicated, the temperature-resolved structural and spectroscopic studies paint a different picture in which rich polymorphism in the solid state occurs between tetragonal (paraelastic) and triclinic (ferroelastic) crystal phases: I (P42/n) → II (P1̅) at 272/277 K (cooling/heating), II (P1̅) → III (P1̅) at 207 K, and III (P1̅) → IV (P1) at 98/127 K. The ferroelectric properties of phase IV have been confirmed by the pyroelectric current and hysteresis loop measurements; additionally, the acentric symmetry has been further supported by second harmonic generation measurements. Crystallographic analysis of phase III reveals the antiparallel alignment of acetamidinium dipoles, pointing to the antiferrroelectric nature of this phase. In turn, the character of the ferroelectric transition (III → IV) should be considered as “displacive” for both cationic and anionic substructures.) In this report, we also explore the two-photon absorption property of ABB at 800 nm, a property that is unexplored for any halobismuthate(III) thus far. We also present periodic ab initio calculations for ABB crystals. The Berry-phase approach at the Hartree–Fock and density functional theory (DFT-D3) method levels is employed for spontaneous polarization calculations. The origin of ferroelectric polarization is studied using DFT-D3 and RHF electronic structure calculations, emphasizing the relationship between Ps and the relative orientation of organic/inorganic components.

Reversing Benzene/Cyclohexane Selectivity through Varying Supramolecular Interactions Using Aliphatic, Isoreticular MOFs.

Effective solid-state adsorbent materials, such as metal organic frameworks (MOFs), rely upon tailored void spaces for selective adsorption of one component from a mixture. This is particularly crucial when separating challenging mixtures such as benzene (Bz) and cyclohexane (Cy) requiring a highly expensive and energy intensive process. Employing bulky "3D-linkers" to construct MOFs leads to materials with unique, contoured pore shapes which consequently allow for significant control over guest adsorption preferences. Investigation into these selectivity preferences is key to identifying suitable materials for industrial separations and is an area currently underexplored. Here, we provide an in-depth investigation exploring the selectivity path between planar and 3D-linkers and their preference to adsorb either Cy or Bz. To validate this principle, the adsorption selectivity of Cy and Bz in 3DL-MOF-1 ([Zn4O(pdc)3] (pdc = bicylo[1.1.1]pentane-1,3-dicarboxylate), CUB-5, and MOF-5 was explored. MOF-5 exhibits a selective preference for Cy adsorption at low pressures, contrary to popular belief, while CUB-5 and 3DL-MOF-1 are Bz selective. DFT-D3 calculations and breakthrough simulations explore this behavior and highlight CUB-5 and MOF-5 as strong candidates for future separation materials.

Competing Effects of Chlorination on the Strength of Te⋅⋅⋅O Chalcogen Bonds Select the Structure of Mixed Supramolecular Macrocyclic Aggregates of Iso-Tellurazole N-Oxides.

Chlorination of 3-methyl-5-phenyl-1,2-tellurazole-2-oxide yielded the λ4 Te dichloro derivative. Its crystal structure demonstrates that the heterocycle retains its ability to autoassociate by chalcogen bonding (ChB) forming macrocyclic tetramers. The corresponding Te⋅⋅⋅O ChB distances are 2.062 Å, the shortest observed to date in aggregates of this type. DFT-D3 calculations indicate that while the halogenated molecule is stronger as a ChB donor it also is a weaker ChB acceptor; the overall effect is that the ChBs in the chlorinated homotetramer are not significantly stronger. However, partial halogenation or scrambling selectively yield the 2 : 2 heterotetramer with alternating λ4 Te and λ2 Te centers, which calculations identified as the thermodynamically preferred arrangement.

Crystal structure from laboratory X-ray powder diffraction data, DFT-D calculations, Hirshfeld surface analysis, and energy frameworks of a new polymorph of 1-benzothiophene-2-carboxylic acid — ERRATUM

Crystal structure from laboratory X-ray powder diffraction data, DFT-D calculations, Hirshfeld surface analysis, and energy frameworks of a new polymorph of 1-benzothiophene-2-carboxylic acid — ERRATUM - Volume 36 Issue 3

Optical and electronic properties of TiO2/GOQDs composites: A combined experimental and first-principles calculations study

In this work, the optical and electronic properties of a TiO2/graphene oxide quantum dots (GOQDs) composite were studied by experimental and computational methods. The experimental procedures were made on TiO2 and GOQDs nanoparticles synthesized by a sol-gel method and one-pot electrochemical carbonization, respectively. The characterization of these materials and the TiO2/GOQDs composite was made using field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS), FT-IR spectroscopy, and dynamic light scattering (DLS). The experimental measurements of the optical properties of these materials by UV–Vis absorption spectroscopy indicate that the addition of GOQDs promotes the expansion of the radiation absorption of TiO2 towards the visible range. Similarly, photoelectrochemical tests performed to determine the electronic properties show that GOQDs improve the separation of the photogenerated electron-hole pairs, increasing the photocatalytic activity of the TiO2. These results were further contrasted with a computational study based on first-principles DFT-D3 calculations, using the projector augmented wave (PAW) method on TiO2, pristine GQDs, GOQDs, TiO2/GQDs, and TiO2/GOQDs clusters. The computational results showed that GOQDs exhibit properties of a p-type semiconductor due to the presence of oxygenated groups. Therefore, when used as TiO2/GOQDs composite, these form a type II heterojunction, increasing the photocatalytic activity of the material.

Structure Determination of Multicomponent Crystalline Phases of (S)-Ibuprofen and l-Proline from Powder X-ray Diffraction Data, Augmented by Complementary Experimental and Computational Techniques

Two multicomponent crystalline phases of (S)-ibuprofen and l-proline with 1:1 stoichiometry are reported, specifically a nonsolvate phase (Ibu-Pro) and a quarter-hydrate phase (Ibu-Pro-QH). Ibu-Pro was prepared only by solid-state mechanochemical synthesis, while Ibu-Pro-QH was obtained both by solution-state crystallization and by solid-state mechanochemistry. The crystal structures of Ibu-Pro and Ibu-Pro-QH were determined directly from powder X-ray diffraction (XRD) data, with structure solution carried out using the direct-space strategy (implemented with a genetic algorithm search procedure) and structure refinement carried out using the Rietveld method. The process of structure determination from powder XRD data was augmented by information from other complementary techniques, specifically solid-state NMR spectroscopy, thermal analysis methods, and periodic DFT-D calculations. A preliminary powder XRD study of the dehydration behavior of Ibu-Pro-QH at elevated temperature is also reported.

The impact of an external electric field on methanol adsorption on XB11N12 (X=B, Co, Ni) nano-cages: A DFT and TD-DFT study

DFT-D3 and TD-DFT calculations at B3LYP/6–311 + g(d) level of theory are employed to study the influence of the TM (Co and Ni) doping, the adsorption of CH3OH, and the external electric field (EF) on the electronic and optical properties of B12N12. The results are analyzed in point of view of BSSE corrected adsorption energies, the density of states (DOS), NBO atomic charges, and UV–vis spectra. The obtained values of dipole moment, ionization potential, chemical potential, hardness, and electrophilicity verified that the doped TM-boron nitride nano-cages are more reactive than the pure B12N12 nano-cage as well the TMB11N12 nano-cages are more reactive than TMB12N11 nano-cages. Additionally, the doping decreases the HOMO-LUMO gap energy gap to 55% and 30% and enhances the adsorption energy by 41.4% and 44.1% for CoB11N12 and NiB11N12 nano-cages, respectively. The adsorption of CH3OH reduces the HOMO-LUMO gap for the B12N12 and enlarge that for the TMB11N12. The value and the direction of the applied EF control the adsorption energy, sensitivity, response time, and recovery time. The TD-DFT calculations declare that the CH3OH adsorption on CoB11N12 and NiB11N12 under the influence of the EF causes considerable shifts for the λmax value in the visible region. Thus, the obtained results may be fruitful for designing an electrical and optical sensor for CH3OH utilizing pure and doped boron nitride nano-cages.

A 3D-RISM-KH study of liquid nitromethane, nitroethane, and nitrobenzene as solvents

The reference interaction site model (RISM) has been applied to explore the liquid state structure of three nitro-compounds, viz. nitromethane, nitroethane, and nitrobenzene. Different dimeric forms of these pure liquids have been located using DFT-D3 calculations in the continuum as well as via RISM calculations. These dimeric forms are held together by weak hydrogen bonds and van der Waals interactions. The solvation energy of solutes in the three aforementioned solvents have been calculated and compared with the experimental data.