Dispersion-corrected Density Functional Theory Research Articles

Internal Energy Dependence of the Pyrrole Dimer Cation Structures Formed in a Supersonic Plasma Expansion: Charge-Resonance and Hydrogen-Bonded Isomers.

The structures of the pyrrole dimer cation (Py2+) formed in an electron-ionization-driven supersonic plasma expansion of Py seeded in Ar or N2 are probed as a function of its internal energy by infrared photodissociation (IRPD) spectroscopy in a tandem mass spectrometer. The IRPD spectra recorded in the CH and NH stretch ranges are analyzed by dispersion-corrected density functional theory (DFT) calculations at the B3LYP-D3/aug-cc-pVTZ level. The spectra of the cold Ar/N2-tagged Py2+ clusters, Py2+Ln (n = 1-5 for Ar, n = 1 for N2), indicate the exclusive formation of the most stable antiparallel π-stacked Py2+ structure under cold conditions, which is stabilized by charge-resonance interaction. The bare Py2+ dimers produced in the ion source have higher internal energy, and the observation of additional transitions in their IRPD spectra suggests a minor population of less stable hydrogen-bonded isomers composed of heterocyclic Py/Py+ structures formed after intramolecular H atom transfer and ring opening. These intermolecular isomers differ from the chemically bonded structures proposed earlier in the analysis of IRPD spectra of Py2+ generated by VUV ionization of neutral Pyn clusters.

Computational Insights into Cyclodextrin Inclusion Complexes with the Organophosphorus Flame Retardant DOPO

Cyclodextrins (CDs) were used as green char promoters in the formulation of organophosphorus flame retardants (OPFRs) for polymeric materials, and they could reduce the amount of usage of OPFRs and their release into the environment by forming [host:guest] inclusion complexes with them. Here, we report a systematic study on the inclusion complexes of natural CDs (α-, β-, and γ-CD) with a representative OPFR of DOPO using computational methods of molecular docking, molecular dynamics (MD) simulations, and quantum mechanical (QM) calculations. The binding modes and energetics of host:guest inclusion complexes were analyzed in details. α-CD was not able to form a complete inclusion complex with DOPO, and the center of mass distance host:guest distance amounted to 4–5 Å. β-CD and γ-CD allowed for a deep insertion of DOPO into their hydrophobic cavities, and DOPO was able to frequently change its orientation within the γ-CD cavity. The energy decomposition analysis based on the dispersion-corrected density functional theory (sobEDAw) indicated that electrostatic, orbital, and dispersion contributions favored host:guest complexation, while the exchange–repulsion term showed the opposite. This work provides an in-depth understanding of using CD inclusion complexes in OPFRs formulations.

Unveiling potential of thiophene-functionalized C3N3 nanosheet as an anode for Li-ion batteries: A DFT-D3 study

Covalent triazine frameworks (CTFs) are a fascinating type of porous organic materials that exhibit numerous distinct features, such as significant specific surface area, outstanding chemical/thermal stability, and structural modifiability at the molecular level. These features make CTFs highly appealing for utilization in Li-ion batteries (LIBs). However, their low electronic conductivity limits their practical applications. In the present study, the potential anode application of thiophene-functionalized C3N3 nanosheet for LIBs was conducted by dispersion-corrected density functional theory (DFT-D3) calculations. It was found that functionalization of the C3N3 nanosheet with six thiophene groups ((THP)6@C3N3) led to the highest reduction (0.19 eV) in the energy gap of the pristine C3N3 nanosheet. A single Li-ion preferably adsorbs between two nitrogen atoms of the triazine ring with an adsorption energy of about 4.59 eV. The absorption of Li-ion resulted in a reduction of the band gap from 1.37 eV to 0.43 eV, indicating enhanced electrical conductivity and superior cycle stability. The fully loaded functionalized nanosheet with nineteen Li-ions at various adsorption sites exhibited a remarkable theoretical specific capacity of 526.55 mAh/g. This configuration also displayed a low open-circuit voltage (0.09 V) and diffusion energy barrier (0.35 eV), ideal as an anode with a rapid charging/discharging rate. Therefore, thiophene-functionalized C3N3 nanosheet demonstrates superior anode performance for LIBs due to its high theoretical specific capacity, small diffusion barrier, and low working voltage. This work can provide insights for the refere development of CTF-based anode materials.

A striking exploration of defect engineering in HfS2, HfSe2, and janus HfSSe through ab initio analysis for HER catalysis application

The present study emphasizes the enhancement in catalytic activity due to the formation of vacancies using dispersion corrected density functional theory. We observed that without vacancy formation, in general the edge site is an active site for hydrogen adsorption, while the lowest Gibbs free energy (ΔGH) is found to be for Janus HfSSe at the S-edge site. Furthermore, interestingly, due to the hindrance of the edge site, it facilitates only the Volmer-Heyrovsky reaction rather than the Volmer-Tafel. Among the mono vacancies, the Hafnium mono vacancy shows the lowest adsorption energy.We observed a competition between the evolution of H2S and H2 gas in the case of HfS2-VHf, whereas in the case of defected Janus and HfSe2, due to the presence of Se layers, we observed no competitiveness with H2S or H2Se gas with hydrogen gas. These defected materials exhibit lower reactional Gibbs free energy than a pristine monolayer due to its metallic nature. We observed that Hafnium vacancy enhances the HER activity, and pave the way for dominating Volmer-Heyrovsky reaction.

Exploring Curcumin Interaction with PLGA Nanoparticles via Various Functional Groups: A Dispersion-Corrected Density Functional Theory and Molecular Dynamics Simulation Approach

Density functional theory (DFT)-D3 dispersion corrections and molecular dynamic (MD) techniques were used to research how curcumin (CUR) and poly (lactic-co-glycolic acid) (PLGA) interact in the water phase. Relaxation based on machine learning (ML) algorithms was used to identify the state configuration that was the most stable. The electronic, optical, and infrared (IR) vibrational properties of the studied configurations were then computed. The findings show that since PLGA nanoparticle can transport CUR via chemical interactions, the binding energy of CUR through carbonyl group to PLGA is about -1.092eV (complex A). The theoretical IR spectrum supports the observation that the functional groups of CUR interacting with PLGA undergo changes, which is consistent with the experimental data. Hence, the Bader charge analysis indicates a charge of about 0.14 (complex A) and 0.17 (complex B) |e| transferred from the PLGA to CUR. The charges in CUR exhibit strong charge transfer to the PLGA structure. The calculated results of the CUR-PLGA complex match the main peak in the 500-580nm range observed in experiments, and the stable optimal optical absorption diagram aligns with the reported spectra. The total density of states (TDOS) of the studied configurations shows that CUR is having an impact on the HOMO and LUMO levels. The PLGA nanoparticle demonstrates a higher sensitivity (86%) towards the presence of CUR in complex D compared to complex B (67%), which can be attributed to the change in the energy gap. This low adsorption energy and high sensitivity suggest that the PLGA nanoparticle indicates its potential to serve as both a carrier and a sensor for detecting CUR in the water phase.

Hydrogen bonds and elastic anisotropy of nitrile molecular crystals: an investigation from first-principles

ABSTRACT Atomistic calculations based on semi-classical dispersion-corrected density functional theory were performed to investigate bonding and elastic properties of low temperature polymorphs of three nitrile molecular crystals. For that purpose, the DFT-PBE-D3ijk method, which account for both pair and three-body interactions, was applied. The analysis of Hirshfeld surfaces demonstrated that the (C-N…H) hydrogen bonds are the strongest and the dominant ones in the three nitrile molecular crystals. The latter were found to share a common structural feature, consisting of an antiparallel orientation of the terminal nitrile groups at their constituent molecules. Our prediction of the elastic properties demonstrated that malonitrile has the highest Young modulus and succinonitrile has the lower one. The three nitrile crystals are expected to have similar resistance to volume variation while succinonitrle is predicted to exhibit the lowest resistance to shape change. Otherwise, succinonitrile was found to be ductile while malononitrile and acetonitrile were shown to be brittle. Elasticity anisotropy analysis demonstrated that the directions of maximum Young’s modulus are always nearly parallel to the direction of alignment of strong (C-H…N) hydrogen bonds in the three nitrile crystals. The present analyses are relevant for understanding the structure and the properties of more complex high temperature phases.

Quantum scattering of icosahedron fullerene C60 with noble-gas atoms

There exist multiple ways to cool neutral molecules. A front runner is the technique of buffer gas cooling, where momentum-changing collisions with abundant cold noble-gas atoms cool the molecules. This approach can, in principle, produce the most diverse samples of cold molecules. We present quantum mechanical and semiclassical calculations of the elastic scattering differential cross sections and rate coefficients of the C60 fullerene with He and Ar noble-gas atoms in order to quantify the effectiveness of buffer gas cooling for this molecule. We also develop new three-dimensional potential energy surfaces for this purpose using dispersion-corrected density functional theory (DFT) with counterpoise correction. The icosahedral anisotropy of the molecular system is reproduced by expanding the potential in terms of symmetry-allowed spherical harmonics. Long-range dispersion coefficients have been computed from frequency dependent polarizabilities of C60 and the noble-gas atoms. We find that the potential of the fullerene with He is about five times shallower than that with Ar. Anisotropic corrections are very weak for both systems and omitted in the quantum scattering calculations giving us a nearly quantitative estimate of elastic scattering observables. Finally, we have computed differential cross sections at the collision energies used in experiments by Han et al. (Chem Phys Lett 235:211, 1995), corrected for the sensitivity of their apparatus, and we find satisfactory agreement for C60 scattering with Ar.

A Highly Stable Microporous Calcium-Based MOF for C2H2/CO2 Separation with Low Regenerative Energy.

Most of the porous materials used for acetylene/carbon dioxide separation have the problems of poor stability and high energy requirements for regeneration, which significantly hinder their practical application in industries. Here, we report a novel calcium-based metal-organic framework (NKM-123) with excellent chemical stability against water, acids, and bases. Additionally, it has exceptional thermal stability, retaining its structural integrity at temperatures up to 300 °C. This material exhibits promising potential for separating C2H2 and CO2 gases. Furthermore, it demonstrates an adsorption heat of 29.3 kJ mol-1 for C2H2, which is lower than that observed in the majority of MOFs used for C2H2/CO2 separations. The preferential adsorption of C2H2 over that of CO2 is confirmed by dispersion-corrected density functional theory (DFT-D) calculations. In addition, the potential of industrial feasibility of NKM-123 for C2H2/CO2 separation is confirmed by transient breakthrough tests. The robust cycle performance and structural stability of NKM-123 during multiple breakthrough tests show great potential in the industrial separation of light hydrocarbons.

Precise structure and energy of group 6 transition metal dichalcogenide homo- and heterobilayers in high-symmetry configurations

Two-dimensional group 6 transition metal dichalcogenide (2D TMDC) bilayers show various high-symmetry stacking configurations, which have also been observed in extended domains formed in their twisted homo- and heterobilayers. The interlayer energy varies for these stacking configurations, and the energy differences determine the relative size of the stacking domains. Therefore, the precise prediction of the composition- and stacking-dependent interlayer energy is crucial to model the domain structure of 2D TMDCs in their twisted bilayer homo- and heterostructures. For the validation of approximate methods that are necessary to tackle these systems encompassing thousands of atoms precise reference data is still lacking. Here, we employ the random phase approximation (RPA) on previously validated SCAN-rVV10 geometries to obtain interaction energies of state-of-the-art accuracy on the six high-symmetry stacking configurations ( Hhh , HhM , HhX , Rhh , RhM , and RhX ) of MX2 (M = Mo, W; X = S, Se) bilayers and compare them with the dispersion-corrected density-functional theory (DFT) functionals Perdew–Burke–Ernzerhof (PBE)+D3(BJ), PBE-rVV10L, and SCAN-rVV10. We identify SCAN-rVV10 as most reliable DFT variant with an average deviation of 1.2 meV/atom in relative energies from the RPA reference, and a root mean squared error of less than 2 meV/atom for interlayer interaction energies. We find interlayer distances obtained by PBE+D3(BJ) as being too short, with an impact on the electronic structure, resulting in the incorrect prediction of the band gap character in some cases. A further result of this work is the significant lowering of the interlayer energy and increasing of the interlayer distance in the high-energy stacking configurations. These stackings can be accessible via shear strain and promote exfoliation.

Optimizing Trace Acetylene Removal from Acetylene/Ethylene Mixture in a Flexible Metal-Organic Framework by Crystal Downsizing.

Improving the gas separation performance of metal-organic frameworks (MOFs) by crystal downsizing is an important but often overlooked issue. Here, we report three different-sized flexible ZUL-520 MOFs (according to the crystal size from large to small, the three samples are, respectively, named ZUL-520-0, ZUL-520-1, and ZUL-520-2) with the same chemical structure for optimizing trace acetylene (C2H2) removal from acetylene/ethylene (C2H2/C2H4) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C2H2 uptake of 4.8 mmol/g at 100 kPa, while the C2H2 uptake at 1 kPa increased with a downsizing crystal. The C2H2 uptake of activated ZUL-520-2 (denoted as ZUL-520-2a) at 1 kPa was ∼55% higher than that of activated ZUL-520-0 (denoted as ZUL-520-0a). The adsorption isotherms and adsorption kinetics validated that gas adsorptive separation is governed not only by adsorption thermodynamics but also by adsorption kinetics. In addition, all three different-sized ZUL-520a MOFs showed high C2H2/C2H4 selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C2H2 adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C2H2/C2H4 (1/99, v/v) mixture and the C2H4 productivity obtained by ZUL-520-2a was much higher than that by ZUL-520-0a. Our work may provide an easy but powerful strategy for upgrading the performance of gas adsorptive separation in MOFs.

Surface Engineering of the Mechanical Properties of Molecular Crystals via an Atomistic Model for Computing the Facet Stress Response of Solids.

Dynamic molecular crystals are an emerging class of crystalline materials that can respond to mechanical stress by dissipating internal strain in a number of ways. Given the serendipitous nature of the discovery of such crystals, progress in the field requires advances in computational methods for the accurate and high-throughput computation of the nanomechanical properties of crystals on specific facets which are exposed to mechanical stress. Here, we develop and apply a new atomistic model for computing the surface elastic moduli of crystals on any set of facets of interest using dispersion-corrected density functional theory (DFT-D) methods. The model was benchmarked against a total of 24 reported nanoindentation measurements from a diverse set of molecular crystals and was found to be generally reliable. Using only the experimental crystal structure of the dietary supplement, L-Aspartic acid, the model was subsequently applied under blind test conditions, to correctly predict the growth morphology, facet and nanomechanical properties of L-Aspartic acid to within the accuracy of the measured elastic stiffness of the crystal, 24.53 ± 0.56 GPa. This work paves the way for the computational design and experimental realization of other functional molecular crystals with tailor-made mechanical properties.

Electrochemical reduction of cyanide on conjugated copper-organic framework Cu3(HHTP)2 monolayer: A dispersion-corrected DFT investigation

Cyanide containing wastewater can cause livestock death and reduce agricultural production and electrochemical reduction of cyanide (CNRR) is a promising way to eliminate its harm and turn waste into valuable products. However, the reaction mechanism and function of electrocatalysts for CNRR have not been fully understood yet. Herein we identify a two-dimensional (2D) conductive copper-organic framework based on triphenylene (Cu3(HHTP)2) for CNRR according to the computed results from dispersion-corrected density-functional theory (DFT-D). Relatively low limiting potential (0.10 V) and high theoretical Faradaic efficiency (near 100%) were found for Cu3(HHTP)2 in the CNRR process, indicating a pretty good performance of Cu3(HHTP)2 monolayer as an electrocatalyst. Mechanism investigations were carried out and both cyanide N-end and C-end-on adsorption patterns as well as nine possible pathways were explored. Appreciable charge density transfer and the enhanced chemical interactions between Cu and C or N atoms are responsible for the outstanding performance of Cu3(HHTP)2 monolayer. The results reveal that the products of CNRR are a gaseous mixture of CH3CH2, NH3 and CH4 at a lower negative-electrode-potential (−0.27 V < U < −0.10 V) while gaseous NH3 and CH4 become main products at a higher negative-electrode-potential (−1.36 V < U < −0.27 V). This work demonstrates that reaction mechanism analysis is a useful approach to identify the catalyst activity and final products of a reaction.

Effect of Interlayer Bonding on Superlubric Sliding of Graphene Contacts: A Machine-Learning Potential Study.

Surface defects and their mutual interactions are anticipated to affect the superlubric sliding of incommensurate layered material interfaces. Atomistic understanding of this phenomenon is limited due to the high computational cost of ab initio simulations and the absence of reliable classical force-fields for molecular dynamics simulations of defected systems. To address this, we present a machine-learning potential (MLP) for bilayer defected graphene, utilizing state-of-the-art graph neural networks trained against many-body dispersion corrected density functional theory calculations under iterative configuration space exploration. The developed MLP is utilized to study the impact of interlayer bonding on the friction of bilayer defected graphene interfaces. While a mild effect on the sliding dynamics of aligned graphene interfaces is observed, the friction coefficients of incommensurate graphene interfaces are found to significantly increase due to interlayer bonding, nearly pushing the system out of the superlubric regime. The methodology utilized herein is of general nature and can be adapted to describe other homogeneous and heterogeneous defected layered material interfaces.

Computational characterization of novel nanostructured materials: A case study of NiCl[formula omitted

A computational approach combining dispersion-corrected density functional theory (DFT) and classical molecular dynamics is employed to characterize the geometrical and thermomechanical properties of a recently proposed 2D transition metal dihalide NiCl2. The characterization is performed using a classical interatomic force field whose parameters are determined and verified through the comparison with the results of DFT calculations. The developed force field is used to study the mechanical response, thermal stability, melting and solidification of a NiCl2 monolayer on the atomistic level of detail. The 2D NiCl2 sheet is found to be thermally stable at temperatures below its melting point of ∼695 K. At higher temperatures, several subsequent structural transformations of NiCl2 are observed, namely a transition into a porous 2D sheet and a 1D nanowire. The MD simulations of NiCl2 cooling show that the molten NiCl2 system solidifies into an amorphous porous 2D structure at T∼450 K. The resulting structure has lower cohesive energy with respect to the initial 2D sheet. The computational methodology presented through the case study of NiCl2 can also be utilized to study the properties of other novel 2D materials, including recently synthesized NiO2, NiS2, and NiSe2.

Theoretical study of NO/CO/O2 gas separation using graphdiyne and boron-doped graphdiyne membranes – A new corresponding state principle

The adsorption and permeance of O2, NO and CO gases on graphdiyne (GDY) and boron-doped graphdiyne (B-doped GDY) surfaces are modeled and studied. Dispersion-corrected density functional theory (DFT) calculation combined with the Climbing Image Nudged Elastic Band (CI-NEB) method was used to elucidate the gas/membrane adsorption energy, equilibrium distance and energy barrier of the studied gases passing through the membranes. It is revealed that the selectivity of B-doped GDY to NO is much greater than that of GDY. Based on selectivity and permeability values, high separation efficiency of NO can be achieved by lowering B-doped GDY temperature below 100 K. In addition, using the corresponding principle, a general expression for the dimensionless permeance of gases in terms of reduced temperature is introduced, which helps us to find an industrially acceptable value of permeance for each gas at a given pressure.

Determination of two structures of the solvent 3-hydroxypropionitrile crystallized at low temperatures

The title compound, 3-hydroxypropionitrile, was crystallized repeatedly in situ inside a quartz capillary using a liquid nitrogen cryostream. The X-ray powder diffraction patterns obtained indicated the presence of two distinct crystalline phases. The cleanest datasets for each of the phases were used to solve the crystal structures via simulated annealing, followed by refinement and optimization via dispersion-corrected density functional theory (DFT) calculations, with a final Rietveld refinement against the experimental data. The two structures appear to correspond to those proposed in a 1960s literature vibrational spectroscopy paper, one being the more stable with a gauche molecular conformation and the second metastable phase more complex with mixed conformations. Dispersion-corrected DFT computation using lattice parameters for both phases obtained from a single 84 K dataset with co-existing phases shows the stable and metastable phases to differ in energy by less than 0.5 kJ mol−1. A comparison of experimental far infrared spectra published in the 1960s with those calculated from the proposed crystal structures provides some independent supporting evidence for the proposed structures.

Studying the adsorption of emerging organic contaminants in zeolites with dispersion-corrected density functional theory calculations: From numbers to recommendations.

Adsorption energies obtained from dispersion-corrected density functional theory (DFT) calculations show a considerable dependence on the choice of exchange-correlation functional and dispersion correction. A number of investigations have employed different approaches to compute adsorption energies of small molecules in zeolites, using reference values from high-level calculations and/or experiments. Such comparative studies are lacking for larger functional organic molecules such as pharmaceuticals or personal care products, despite their potential relevance for applications, e. g., in contaminant removal or drug delivery. The present study aims to fill this gap by comparing adsorption energies and, for selected cases, equilibrium structures of emerging organic contaminants adsorbed in MOR- and FAU-type all-silica zeolites. A total of 13 dispersion-corrected DFT approaches are compared, including methods using a pairwise dispersion correction as well as non-local van der Waals density functionals. While absolute values of adsorption energies vary widely, qualitative trends across the set of zeolite-guest combinations are not strongly dependent on the choice of functional. For selected cluster models, DFT adsorption energies are compared to reference values from coupled cluster (DLPNO-CCSD(T)) calculations. Although all DFT approaches deliver systematically more negative adsorption energies than the coupled cluster reference, this tendency is least pronounced for the rev-vdW-DF2 functional.

Three-dimensional covalent organic frameworks with nia nets for efficient separation of benzene/cyclohexane mixtures

The synthesis of three-dimensional covalent organic frameworks with highly connected building blocks presents a significant challenge. In this study, we report two 3D COFs with the nia topology, named JUC-641 and JUC-642, by introducing planar hexagonal and triangular prism nodes. Notably, our adsorption studies and breakthrough experiments reveal that both COFs exhibit exceptional separation capabilities, surpassing previously reported 3D COFs and most porous organic polymers, with a separation factor of up to 2.02 for benzene and cyclohexane. Additionally, dispersion-corrected density functional theory analysis suggests that the good performance of these 3D COFs can be attributed to the incorporation of highly aromatic building blocks and the presence of extensive pore structures. Consequently, this research not only expands the diversity of COFs but also highlights the potential of functional COF materials as promising candidates for environmentally-friendly separation applications.

A DFT study for the detection of CH2O gas by using ZnONTs

In the past few decades, the removal of organic solvents from different substances, especially through the use of nanostructured materials, has been crucial in various industries, including improvement of innovative and adaptable nano adsorbents. Computational approaches are widely recognized as powerful tools for searching molecular systems at atomic level and investigating the characteristics of their interactions. This study utilized the dispersion-corrected DFT approach to gain a detailed comprehension of how CH2O molecules interact with both Pd-doped and pristine ZnO nanotubes (ZnONTs) during the adsorption process. The aim was to achieve a comprehensive comprehension of the adsorption behavior. To accomplish this, an extensive examination of the active sites and optimized geometrical characteristics of interacting systems was conducted. To assess adsorption capacity of Pd-ZnO nanotube and pristine ZnO nanotube for CH2O, binding characteristics of the interacting species have been assessed. This evaluation included analyzing the interaction energy (Eint), charge transfer, electronic properties, and ELF analysis. Moreover, Pd-doping greatly enhances the adsorption strength of ZnONTs, thereby imparting them with superior capability for CH2O adsorption. The significant adsorption strength of CH2O by the sensor under consideration raises the prospect of utilizing these nanotubes as highly effective sensor materials for CH2O detection, which is a matter of great interest. The results of our study provide a foundation for designing innovative and energy-efficient nanosensors that can serve as cost-effective solutions for detecting contaminants in wastewater.

Linking experimental findings and theoretical insights on the mechanochemical synthesis of PbTe quantum dots: The effect of ethylene glycol

It is provided a new pathway for obtaining the formation of small dimensional PbTe nanostructures during milling, including quantum dots (QDs). It is possible via the addition of ethylene glycol (EG) which is the key factor to decide the final morphology and size of small dimensional PbTe nanostructures. Therefore, in this work, the effects of EG, as a process control agent (PCA), on the growth mechanisms of PbTe QDs are experimental and theoretically investigated. To achieve this goal, the behavior between EG and inorganic PbTe interface interactions is explored via density functional theory (DFT). The occurrence of PbTe is detected by using X-ray diffraction technique and the mechanical kneading suppression is verified through electron microscopy results. The formation of rounded and quasi faceted PbTe QDs are ruled by structural-defect and imperfect oriented attachment mechanisms respectively, which are strongly evidenced by high-resolution transmission electron microscopy. Interactions between EG and low-index surfaces are modeled by dispersion-corrected DFT calculations. Through the electrostatic potential mapped on the van der Waals isosurfaces, adsorption modes of the selected PCA on the PbTe surface are proposed, allowing rationalizing the facets exposed by the PbTe QDs after the surface treatment. Changes induced by the EG molecule, as PCA, are rationalized in terms of surface energy. Interactions with the PbTe surfaces stabilize the (100) facet, while destabilize the (111) facet. Wulff constructions support the formation of particles, in the nanometric scale, with cubic or cubic with rounded edges.