Combined Density Functional Theory Research Articles

Self-consistent quasiparticle GW and hybrid functional calculations for Al/InAs/Al heterojunctions: Band offset and spin-orbit coupling effects

The electronic structure of surfaces and interfaces plays a key role in the properties of quantum devices. Here, we study the electronic structure of realistic Al/InAs/Al heterojunctions using a combination of density functional theory with hybrid functionals and state-of-the-art quasiparticle GW (QSGW) calculations. We find a good agreement between QSGW calculations and hybrid functional calculations, which themselves compare favorably well with angle-resolved photoemission spectroscopy experiments. Our paper confirms the need for well-controlled quality of the interfaces to obtain the needed properties of InAs/Al heterojunctions. A detailed analysis of the effects of spin-orbit coupling on the spin splitting of the electronic states shows a linear scaling in k space, related to the two-dimensional nature of some interface states. The good agreement by QSGW and hybrid functional calculations opens the door towards trustable use of an effective approximation to QSGW for studying very large heterojunctions. Published by the American Physical Society 2024

Generation of Surface Ga-H Hydride and Reactivity toward CO2.

Hydrogen adsorption on gallium oxide was investigated by in situ infrared (IR) spectroscopy over a temperature range of 30-450 °C. Both hydroxyl groups and Ga-H hydrides with a pair of characteristic bands at 3685 (3532) cm-1 and 2011 (1988) cm-1 were detected on the surface gallium oxide. The formation and stability of surface Ga-H hydrides were found to be highly dependent on the temperature of H2 dissociation. Through a combination of density functional theory (DFT) calculations and isotopic experiments, a mechanism involving both heterolytic and homolytic pathways for hydrogen dissociation was proposed for the generation of Ga-H hydrides. Furthermore, the reactivity of surface Ga-H hydrides was explored by their interactions with various probe molecules such as carbon dioxide, oxygen, and nitrogen. A potential reaction mechanism involving the attraction between nucleophilic hydrogen and positively charged intermediates was suggested during those hydrogenations.

DFT and Monte Carlo simulation studies of potential corrosion inhibition properties of some basic heterocyclic compounds

ABSTRACT This study utilises a combination of density functional theory (DFT) approach, 6-31G (d, p) basis set, and Monte Carlo (MC) simulations. The goal is to understand the relationship between the structure and properties of heterocyclic inhibitors and how they interact with Fe (110) surfaces. Furan, pyrrole, thiophene, pyridine, pyridazine, pyrimidine, indole, benzofuran, carbazole, quinolone, isoquinoline, and imidazole are the chemicals that were looked at in this study. The DFT calculations provide important insights into various properties of the inhibitors, such as molecular structure, dipole moments, electrostatic potential maps, Reduced Density Gradient (RDG), UV spectroscopy, and thermal characteristics. Carbazole has the smallest energy difference (4.789 eV) and the highest softness (0.209 eV−1), It also has the most chemical activity, Furthermore, the Monte Carlo models demonstrate that these derivatives have favourable adsorption energies on the Fe (110) surface. Among them, carbazole shows significant inhibitory potential. The study confirms that the carbazole compound with the biggest negative adsorption energy (−95.495) actually has the smallest energy difference and fits with the MC simulation for adsorption on Fe (110) when it is not charged. Carbazole has much stronger adsorption than oxazole, showing how the structure of a molecule affects how well an inhibitor works.

S-type Bi2S3/BiOBr heterojunction with robust piezo-photocatalytic dye removal activity: degradation performance and mechanism investigation

In this work, an efficient S-type Bi2S3/BiOBr piezo-photocatalysts was prepared by the decoration of Bi2S3 nanorods on the surface of BiOBr nanosheets. The piezo/photo/piezo-photocatalytic performance of samples were evaluated under the irradiation of ultrasonic and/or simulated-sunlight employing methyl orange (MO) as a target reactant, indicating that above catalytic activity of BiOBr is able to be elevated after Bi2S3 attachment. Particularly, the 10%Bi2S3/BiOBr sample exhibits the optimal catalytic performance. It is worth noting that the 10%Bi2S3/BiOBr sample achieves much higher piezo-photocatalytic MO removal efficiency than its photocatalysis and piezocatalysis, demonstrating a remarkable synergistic improvement between piezocatalysis and photocatalysis with a synergistic enhancement factor (SF) of ∼1.29. The formation of S-type heterojunction in the Bi2S3/BiOBr composite was directly confirmed by the combination of density functional theory (DFT) calculation and in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) measurement, elevating the surface separation of generated charges. Meanwhile, the ultrasonic-excited piezoelectric polarization field in BiOBr nanosheets excited by ultrasonic irradiation promotes the bulk segregate of generated charges. Benefiting from above two aspect effects, the overall separation of generated charges can be effectively achieved, leading to outstanding piezo-photocatalytic degradation activity of Bi2S3/BiOBr composite.

Atomistic first-principles modeling of single donor spin-qubit

Using an impurity atom in crystal silicon as a spin-1/2 qubit has been made experimentally possible recently where the impurity atom acts as a quantum dot (QD). Quantum transport in and out of such a donor QD occurs in the sequential tunneling regime where a physical quantity of importance is the charging (addition) energy, which measures the energy necessary for adding an electron into the donor QD. In this work, we present a first-principles method to quantitatively predict the addition energy of the donor QD. Using density functional theory (DFT), we determine the impurity states that serve as the basis set for subsequent exact diagonalization calculation of the many-body states and energies of the donor QD. Due to the large effective Bohr radius of the conduction electrons in Si, very large supercells containing more than 10 000 atoms must be used to obtain accurate results. For the donor QD of a phosphorus impurity in bulk Si, the combined DFT and exact diagonalization predicts the first addition energy to be 53 meV, in good agreement with the corresponding experimental value. For the donor QD of an arsenic impurity in Si, the first addition energy is predicted to be 44.2 meV. The calculated many-body wave functions provide a vivid electronic picture of the donor QD.

σ Interference: Through-Space and Through-Bond Dichotomy.

Dividing orbital interactions into through-space (TS) and through-bond (TB) modes is valuable for understanding various molecular properties. In this paper, we elucidate how the quantum interference phenomenon known as σ interference in electron transport through σ systems arises from TS and TB interactions. We performed electron transport calculations using a combination of density functional theory and nonequilibrium Green's function methods, focusing on ethylenediamine, a classical molecule that effectively highlights the contrast between TS and TB interactions. Our results confirm that destructive σ interference occurs in the syn and gauche conformers of this molecule. To further investigate both TS and TB interactions, we employed two analytical methods: the fragment molecular orbital (FMO) method, which captures the effects of both TS and TB interactions, and the chemical graph theory method, which specializes in TB interactions. The FMO analysis demonstrated that TB interactions lead to the characteristic distribution and energy level alignment of the frontier orbitals. Additionally, it was clarified that a change in TS interaction, due to a variation in the dihedral angle of the molecule, alters the energy gap between these orbitals, resulting in the manifestation of σ interference in the syn and gauche conformers, but not in the trans conformer. The chemical graph theory analysis based on the ladder C model, aimed at exploring the topological origin of σ interference from the network of TB interactions, revealed that σ interference is caused by the cancellation between the walk associated with geminal interactions (σ-conjugation) and the one related to vicinal interaction (σ-hyperconjugation). Notably, it was found that the vicinal interaction, which changes sign with the dihedral angle, has a decisive influence on whether this cancellation occurs. These findings clarify that σ interference arises from the interplay between TS and TB interactions. This insight will be valuable for designing molecular systems that utilize σ interference.

Exploring complete catalytic cycle of methane oxidation to methanol on Cu2O2 stabilized within MIL-53(Al) framework: A combined DFT and microkinetic study

Although inspiration from copper-based natural enzymes has shown promise in improving catalyst design for methane-to-methanol (MTM) oxidation, high productivity, and selectivity under mild conditions remain a significant challenge. This study constructs the dinuclear copper (Cu2) species stabilized within the metal-organic framework (MOF), MIL-53(Al), containing Cu as efficient catalytic sites and explores the ability of different oxidants (O2, N2O, and H2O2) to oxidize Cu2 into the dicopper-oxo (Cu2O2) species using density functional theory (DFT) calculations. Our results indicate the kinetic and thermodynamic favorability of Cu2O2 species formation using O2 as an oxidant within the MIL-53(Al) framework. Furthermore, the thermal stability of Cu2O2/MIL-53(Al) has been verified via ab initio molecular dynamics (AIMD) calculations. The kinetics of the complete MTM oxidation cycle over Cu2O2/MIL-53(Al) have been studied using both DFT and microkinetic simulation methods. The present study predicts that the C-H activation on the Cu2O2/MIL-53(Al) has a low free energy barrier (0.77 eV) and that the high stability of CH3 and its very low free energy barrier in the C-O coupling step favors the methanol formation over the formaldehyde. More importantly, Cu2O2/MIL-53(Al) exhibits high methanol selectivity owing to the inhibition of CH3 dehydrogenation and low methanol desorption energy (0.21 eV). Microkinetic simulations confirm the methanol production under relatively mild reaction conditions (200–280 K and 1 bar). This work provides insights into the feasibility of selective MTM oxidation over this family of MOF under mild conditions.

Frenkel defects facilitate oriented 1O2 formation in birnessite for enhanced catalytic oxidation of formaldehyde

Defect strategy is one of the most effective approaches for enhancing the efficiency of Mn-based catalysts in removing formaldehyde (HCHO) under ambient conditions. Herein, the interlayer Mn-O octahedra in birnessite synergistically form with Mn vacancies through proton exchange in acidic solutions, creating surface Frenkel defects. As evidenced by highly combined physicochemical characterization and density functional theory calculations, surface Frenkel defects are highly active sites on the surface of birnessite. The surface Frenkel defects can induce surface electronic reconstruction, generating strong electrophilicity, which promotes the evolution of superoxide radicals (O2•−) into singlet oxygen (1O2). In-situ quenching DRIFTS indicates that 1O2 is the most important ROS in the oxidation process of HCHO. Additionally, the surface Frenkel defects enhance the adsorption of HCHO, promoting the dehydrogenation of HCHO to form CO, which is then rapidly oxidized to CO2 and H2O under the action of 1O2. This provide a more effective kinetic and thermodynamic catalytic pathway. The defect-rich birnessite (R-Bir) achieved complete HCHO removal in the dynamic test at 10 ppm within 10 hours, significantly outperforming defect-free birnessite (F-Bir) and most previously reported catalysts. This study precisely reveals the catalytic mechanism of HCHO over R-Bir and provides valuable insights for the design of high-performance environmental catalysts.

Multifaceted insights into pentagonal BeP2 monolayer: From electrochemical to mechanical resilience for alkali-ion batteries using DFT

Herein, we elucidated the properties of a pentagonal BeP2 monolayer, emphasizing its robust dynamic, thermal, and mechanical stabilities, as well as its promising electrochemical characteristics. Combining density functional theory (DFT) with a thermodynamic energy decomposition scheme, we identified BeP2 as a potentially excellent 2D material for energy storage devices. It is characterized by large lattice parameters and semi-metallic behavior, exhibiting a zero density of states (DOS) at the Fermi level. It demonstrates favorable open-circuit voltages, low metal ion migration barriers, and negligible structural modifications for Na and K ions. The specific capacities of Li/Na/K reached remarkable values, surpassing those of most previously reported monolayers. Emerging ion battery technology necessitates solid, directly comparable data to establish an optimized standard organic solvent electrolyte. With this objective in mind, we systematically investigated systems combining two Li/Na/K salts with three different alkyl carbonate solvents. Furthermore, we proposed a defect in BeP2 to explore all possible avenues for sustaining the pentagonal BeP2 monolayer (supplementary Fig. S5 and S6). In summary, our findings strongly indicate that the pentagonal BeP2 monolayer holds considerable promise as an anode material for sodium-ion batteries (NIBs) and potassium-ion batteries (KIBs) owing to its high electrochemical and mechanical sustainability and excellent compatibility with electrolytes.

The enhanced SO2 resistance of Fe-Ti catalyst by W/SO42− co-modification for NH3-SCR: A combined experimental and DFT study

It remains a great challenge to improve the low-temperature SO2 resistance of catalysts applied for selective catalytic reduction of NOx with NH3 (NH3-SCR). This work develops an outstanding SO2-tolerant Fe-Ti (FT) catalyst by W/SO42− co-modification via a sol–gel method using Fe(NO3)3·9H2O, tetrabutyl titanate, ammonium tungstate and thiourea as raw materials. The physicochemical characterizations, in-situ diffuse reflectance infrared Fourier transform (DRIFT) measurements and density functional theory (DFT) calculations were combined to reveal the underlying mechanisms. Although W doping can effectively enhance the surface acidity, NH3 adsorption on Lewis acid sites can still be restrained by competitive adsorption of SO2, whereas SO42− modification can enhance the adsorption stability of NH3 without being affected by SO2. Simultaneously, the NO adsorption ability on Fe sites can be significantly enhanced by W/SO42− co-modification. Furthermore, the W doping or SO42− modification can induce conversion of Fe3+ to Fe2+ to affect the redox property of Fe species. A proper amount of Fe2+ suppressed the oxidizability of FT catalyst to inhibit NH3 overoxidation to enhance N2 selectivity, and created more oxygen vacancies to generate larger amount of chemisorbed oxygen to facilitate NH3 dehydrogenation and NO oxidation. More importantly, the inhibition effect of SO2 adsorption on Fe sites was strengthened by W/SO42− co-modification. Consequently, the W/SO42− co-modified FT catalyst exhibited high activity with >90 % of NO conversion and >95 % of N2 selectivity within a broad window of 275–450 °C and possessed superior SO2 + H2O tolerance at 275 °C.

Cellular Phosphate Sensing and Anion Binding by an Azacrown-Calixpyrrole Hybrid.

A hybrid receptor-sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor-sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (Kassoc H2PO4 ->H2P2O7 2->AMP-≫ADP2- or ATP3- over halides, nitrate, or hydrogen sulfate; all Na+ salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real-time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence-based microscale method compares favorably with the state-of-the-art techniques but can easily be practiced in a high-throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation.

Characterization of glycylglycyltyrosine radical cations: Insights into β-radical formation and N–Cα peptide bond dissociation at the tyrosine residue

We investigated the dissociation and characterization of radical cations of glycylglycyltyrosine [GGY]•+, focusing on β-radical-induced N–Cα peptide bond cleavage reactions at the tyrosyl residue. By combining density functional theory (DFT) calculations with experimental studies utilizing low-energy collision-induced dissociation (CID) mass spectrometry and deuterium labeling on the two β-hydrogen atoms of the tyrosyl residue in [GGY]•+, we elucidated the intricacies of the β-radical structure and its origin. Unlike tryptophan-containing [GGW]•+, which forms canonical π-radical precursors, infrared multiphoton dissociation (IRMPD) spectroscopy results reveal that the β-radical [GGYβ•]+ isomerizes from the phenoxy-radical [GGYo•]+, with the radical localized on the β-carbon of the tyrosyl residue and the phenolic oxygen atom, respectively. The isomerization barriers from [GGYo•]+ to [GGYβ•]+ are <109 kJ mol−1.

Update of the present decomposition mechanisms of ammonia: A combined ReaxFF, DFT and chemkin study

Ammonia, a promising carbon-free fuel, offers significant potential for reducing carbon emissions. The decomposition of NH3 is crucial for improving NH3 combustion, yet its mechanisms remain unclear. This study uses ReaxFF simulations, density functional theory (DFT), and Chemkin calculations to explore NH3 decomposition and refine the Konnov mechanism. Our results show that the NH3 to N2 conversion is highly temperature-dependent. At high temperatures, the pathway is NH3→NH2→N2H4→N2H2→N2. As temperature decreases, the N2H pathway becomes more significant, shifting the reaction to NH3→NH4→NH2→N2H→N2 pathway. Additionally, temperature affects H dissociation: at lower temperatures, NH3 to NH2 follows NH3→NH4→NH2, while the NH4 pathway's influence diminishes with rising temperatures. The updated Konnov mechanism improves NH3 decomposition prediction accuracy by about 72.79% and enhances predictions of decomposition rates and intermediate formations (NH, NH2, NH4). This research advances the understanding of NH3 decomposition mechanisms and is vital for optimizing burners for efficient and stable NH3 combustion.

Effective removal of Pb (II) from wastewater by zinc-iron bimetallic oxide-modified walnut shell biochar: A combined experimental and DFT calculation approach

The modified walnut shell biochar (WBC) was prepared through zinc-iron bimetallic oxide modification (ZF@WBC) at 600 °C under oxygen-limited conditions in this study. Through adsorption experiments, characterization analyses, and density functional theory (DFT) calculations, the adsorption properties of ZF@WBC to Pb (II) were investigated and the mechanism underlying such adsorption was elucidated. Characterization results showed that the surface area (375.9709 m2/g) and total pore volume (0.205319 cm3/g) of ZF@WBC were significantly greater than those of walnut shell biochar. The maximum adsorption capacity of ZF@WBC for Pb (II) was found to be 104.26 mg/g, which is 2.57 times higher than that of WBC according to the adsorption experiments conducted. The observed adsorption behavior followed both the pseudo-second-order (PSO) kinetic model and Langmuir isothermal adsorption model, suggesting that chemisorption plays a major role in the absorption process. Based on SEM, XRD, XPS, FTIR characterizations along with DFT calculations performed in this study, it can be concluded that surface complexation, ion exchange, electrostatic attraction, physical absorption are among the main mechanisms responsible for absorption of Pb (II) by ZF@WBC. Furthermore, even in the presence of interfering ions at different concentrations, ZF@WBC exhibited a removal rate above 70% for Pb (II). Therefore, ZF@WBC has great potential as an effective absorbent for removing Pb (II) from wastewater, while also offering opportunities for biomass waste resource utilization.

Real-Time Simulation of the Reaction Kinetics of Supported Metal Nanoparticles.

A common issue with supported metal catalysts is the sintering of metal nanoparticles, resulting in catalyst deactivation. In this study, we propose a theoretical framework for realizing a real-time simulation of the reactivity of supported metal nanoparticles during the sintering process, combining density functional theory calculations, microkinetic modeling, Wulff-Kaichew construction, and sintering kinetic simulations. To validate our approach, we demonstrate its feasibility on α-Al2O3(0001)-supported Ag nanoparticles, where the simulated sintering behavior and ethylene epoxidation reaction rate as a function of time show qualitative agreement with experimental observation. Our proposed theoretical approach can be employed to screen out the promising microstructure feature of α-Al2O3 for stable supported Ag NPs, including the surface orientation and promoter species modified on it. The outlined approach of this work may be applied to a range of different thermocatalytic reactions other than ethylene epoxidation and provide guidance for the development of supported metal catalysts with long-term stability.

Can ZnO/Cu catalyst provide promising activity for glycerol direct dehydrogenation? A combined density functional theory and coverage-dependent microkinetics study

Non-oxidative dehydrogenation (NODH) reaction of glycerol is a perfect atom economical technical route to produce higher-value 1,3-dihydroxyacetone (DHA). Cu-based catalyst (especially ZnO/Cu system), is known as active species for alcohol dehydrogenation, which may be also promising one for glycerol NODH. In this study, we combine coverage-dependent free energy profile using first-principle calculation, and microkinetic model, to investigate the NODH of glycerol on the ZnO/Cu(111) surface, and a detailed comparison is made with Cu (111) surface. The coverage-dependent microkinetic model takes into account the lateral adsorbate–adsorbate self-interactions and cross-interactions, and their effect on binding energy of both intermediate and transition state. Besides, it guarantees the reaction kinetics is based on the coverage self-consistent between surface model and microkinetic result under practically reaction conditions. Compared with coverage-dependent kinetics simulation (20 %–30 %), coverage-independent model overestimates the DHA selectivity on Cu (111) (over 90 %). Our coverage-dependent kinetics simulation illustrates that both glycerol conversion and DHA selectivity are most determined by the first dehydrogenation step (OH bond scission) of glycerol on Cu (111). However, when ZnO cluster adsorbed on the Cu (111) surface, ZnO cluster promotes the electron transferring between glycerol and Cu sites, which accelerates OH bond scission process of glycerol. Under coverage-dependent microkinetic model, the turnover frequency and selectivity of DHA on ZnO/Cu(111) get much improvement compared with Cu (111). Finally, the superior of ZnO/Cu(111) is further proved by continuous stirred tank reactor simulation, where NODH of glycerol need shorter residence times or lower temperature to reach 100 % conversion, as well as keep higher DHA selectivity.

Harnessing high potential benzothiazole chalcones against dengue virus NS5 protein: A multi-faceted theoretical study through molecular docking, ADME, and DFT

Chalcones bearing tetralone, indanone and benzothiazole cores were synthesized successfully using a general Claisen-Schmidt condensation protocol. The prepared compounds were purified and structurally analyzed by 1H, 13C NMR, and FT-IR techniques. A multi-faceted theoretical approach, combining Density Functional Theory (DFT), molecular docking, and ADME predictions, was employed to evaluate their therapeutic potential. DFT calculations at the B3LYP/def2-TZVP level revealed key electronic properties, with TD3 compound demonstrating the highest chemical reactivity. Molecular Electrostatic Potential (MEP) and Reduced Density Gradient (RDG) analyses provided insights into the compounds' non-covalent interactions and charge distributions. Molecular docking studies against the NS5 protein (PDB: 6KR2) showed superior binding affinities for all three compounds compared to the control ligand SAH, with TD3 exhibiting the lowest binding energy (−8.41 kcal/mol) and theoretical inhibition constant (689.31 nM). ADME predictions indicated favorable drug-like properties with concerns regarding aqueous solubility and potential P-glycoprotein interactions. Toxicity evaluations highlighted challenges, particularly in hepatotoxicity and carcinogenicity. The study identified TD3 as a promising lead compound for Dengue Virus NS5 inhibition, while also emphasizing the need for targeted modifications to address toxicity concerns. This research not only contributes to anti-dengue drug discovery efforts but also provides a robust methodological framework for the theoretical evaluation of similar small compounds in future investigations.

Theoretical insights into laser-assisted field evaporation of ionic compounds

This study addresses the kinetic process of field evaporation of MgO assisted by ultrafast laser pulses combining density functional theory and molecular dynamics. A quantitative model is presented to describe the competitive evaporation of Mg and O ions under various conditions by comparing the activation barriers. The coordination number has a significant impact on the evaporation kinetics. The evaporation ratio of Mg to O rises with increasing DC field strength and laser intensity. Moreover, the energetics of evaporation is in correlation with photo-induced field ionization, revealing distinct mechanisms of evaporation for Mg and O. While Mg undergoes further ionization and field evaporation simultaneously, the evaporation of O is coupled with the relaxation of excited carriers. The final charge state of evaporated O is determined by the DC field strength rather than the laser intensity. Our findings provide insights into laser–matter interactions in ionic compounds and contribute to the development of atom probe techniques.

Computational insight into the selectivity of [formula omitted]-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

The observed difference in the selectivity towards alkane, ketone, and alcohol hydrodeoxygenation products over Ru and Rh catalysts is explored using a combination of density functional theory and microkinetics. Using γ-valerolactone as a model compound, we investigate the reaction mechanism in order to identify selectivity determining species. The effect of the coadsorbed water molecule as well as the higher adsorbate surface coverage on reaction barriers and energies is explored as well. The performed calculations suggest that the desired alkane product is formed from a ketone intermediate on Ru, and through both ketone and alcohol on Rh, although the selectivity towars alkane on Rh is much lower than on Ru.

Exploring the Potential of Beta-Cyclodextrin-Based MIL-101(Cr) for Pharmaceutical Removal from Wastewater: A Combined Density Functional Theory and Molecular Simulations Study.

Pharmaceutical contaminants pose significant risks to ecosystems and human health, necessitating effective removal strategies. This research focuses on developing advanced adsorbents for removing pharmaceutical pollutants from the environment. Metal-organic frameworks (MOFs), specifically MIL-101(Cr) functionalized with biodegradable beta-cyclodextrin (β-CDex), were investigated as potential nanocomposite adsorbents for the removal of ketorolac (KTRK), naproxen (NPXN), and tramadol (TRML). The study employed molecular simulations and density functional theory (DFT) calculations to explore the interactions between the pollutants and adsorbents. Analyses of DFT results, including electrostatic potential, ionization energy, density of states, and molecular orbital analysis, provided insights into the reactivity of pollutants and adsorbents. Additionally, the structural properties of the adsorbents, such as fractional free volume, radius of gyration, and system energies, were thoroughly examined. Molecular dynamics (MD) and Monte Carlo (MC) simulations were used to evaluate the adsorption capacities of MIL-101(Cr) for the target pharmaceutical pollutants. The results demonstrated the superior adsorption performance of the nanocomposite adsorbent, particularly for KTRK, with an adsorption energy of -1934 kcal/mol, compared to the pristine MIL-101(Cr), which had an adsorption energy of -1916 kcal/mol. This enhanced adsorption is attributed to the optimal molecular fit, guest-host solid interactions, and the selective encapsulation capabilities of β-CDex. This research highlights the potential of MOF-based nanocomposites as effective and sustainable solutions for pharmaceutical pollution. By advancing the understanding of molecular interactions through simulations, this study contributes to developing innovative adsorbents for wastewater treatment and the protection of water resources.