Quantum Chemical Density Functional Theory Research Articles

Encapsulating Proton Inside C60 Fullerene: A Density Functional Theory Study on the Electronic Properties of Cationic X+@C60 (X+ = H+, H3O+ and NH4+)

Confining protons into an enclosed carbon cage is expected to give rise to unique electronic properties for both the inner proton and the outer cage. In this work, we systematically investigated the geometric and electronic structures of cationic X+@C60 (X+ = H+, H3O+, and NH4+), and their corresponding neutral species (X = H2O, NH3), by quantum chemical density functional theory calculations. We show that C60 can trap H2O, NH3, H3O+ and NH4+ at the cage center and only slightly influence their geometries. The single proton clings to the inner wall of C60, forming a C-H chemical bond. The encapsulated neutral species almost do not change the electronic structure of the C60, while the internal cations have obvious effects. The charge transfer effect from the inner species to the C60 cage was found for all X@C60 (X = H2O, NH3) (about 0.0 e), X+@C60 (X+ = H3O+, NH4+) (about 0.5 e) and H+@C60 (about 1.0 e) systems. Encapsulating different forms of protons also regulates the fundamental physico-chemical properties of the hollow C60, such as the HOMO-LUMO gaps, infrared spectra, and electrostatic potential, etc., which are discussed in detail. These findings provide a theoretical insight into protons’ applications, especially in energy.

Molecular insights into genistein-NSAID hybrids—synthesis, characterisation and DFT study

AbstractGenistein (GEN) is one of the pharmaceutically valuable phenolic compounds, which belongs to the isoflavone group of flavonoids and is a natural phytohormone found mainly in soybeans and red clover. It affects estrogen receptors, functioning as a selective estrogen receptor modulator (SERM) with anti-inflammatory and antioxidant activity. The presence of reactive phenolic groups in genistein provides an opportunity to expand its structure by introducing components responsible for anti-inflammatory properties. Such an innovative combination of a compound with anticancer and antioxidant potential with an anti-inflammatory compound (NSAID) may lead to interesting new derivatives with dual mechanisms of biological action. The synthesis and characterisation of genistein-NSAID hybrid compounds (ibuprofen, ketoprofen, naproxen, flurbiprofen) was conducted, together with a comprehensive structural and quantum chemistry DFT (density functional theory) computational analysis allowing the description of 1H-NMR and 13C-NMR spectroscopic properties of the starting compounds and the resulting hybrids. The study resulted in the formation of seven hybrid GEN-NSAID derivatives. In the case of ibuprofen, ketoprofen and flurbiprofen, a mixture of isomeric hybrid GEN-4’-NSAID and GEN-7-NSAID derivatives was obtained, whereas, for naproxen, only GEN-4’-NSAID was formed. The structural characteristics of the resulting compounds were determined using MS, IR, 1H-NMR and 13C-NMR spectroscopic methods. The most accurate DFT computational methods for predicting 1H-NMR and 13C-NMR spectra were also established with statistical parameters to assess their accuracy.

Performance Study and Application of Antioxidant Peptides CHCIWM and CHCPWM

AbstractWhen the level of reactive oxygen species (ROS) increases abnormally in the body, it damages tissue cells and is closely related to the occurrence of various chronic diseases. Antioxidant peptides (APs) are a class of active short peptides with antioxidant capacity, which have great research value. In this paper, two APs were designed and synthesized based on the structural features of APs: CHIWM (AP1) and CHCPWM (AP2). The reactive sites and activities of APs were analyzed using the quantum chemical density functional theory (DFT) method. The reactive sites are all located in the indolyl heterocycle of tryptophan residues, among which AP1 has a smaller energy gap and single point energy. Multiple free radical scavenging assays showed that AP1 and AP2 had stronger antioxidant activity than the positive control, glutathione (GSH). For scavenging DPPH free radicals, the IC50s values were 0.613 mg/mL and 0.606 mg/mL, respectively. In cellular assays, both AP1 and AP2 were able to scavenge ROS in the cells and attenuate cellular damage. In conclusion, AP1 and AP2 designed in this paper have good antioxidant activity and have the potential to be applied in the treatment of chronic diseases caused by cellular oxidative damage.

Exploring the Effectiveness of 3-Chloro-4-morpholin-4-yl-1,2,5-thiadiazole as a Eco-Friendly Corrosion Inhibitor for Mild Steel in HCl Solution: Experimental and DFT Analysis

Corrosion is a significant issue in many industries, particularly where metals are exposed to harsh chemical environments. This study investigates the efficacy of 3-Chloro-4-morpholin-4-yl-1,2,5-thiadiazole (CMTD) as a corrosion inhibitor for mild steel in 1 M HCl solution across a temperature range of 303–333 K. Using weight loss measurements, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques, the inhibition efficiency of CMTD was evaluated at different concentrations and temperatures. The results show that CMTD achieves a maximum inhibition efficiency of 96.8% at a highest inhibitor concentration, even at elevated temperatures. The adsorption of CMTD on the mild steel surface follows the Langmuir adsorption isotherm, with a calculated free energy of adsorption (ΔGads) of -39.5 kJ/mol, confirming a spontaneous chemisorption process. Quantum chemical Density Functional Theory (DFT) studies further elucidated the relationship between CMTD's molecular structure and its inhibition efficiency. Key parameters, including the energy gap (Egap = 3.551 eV), highest occupied molecular orbital (EHOMO = -6.317 eV), and lowest unoccupied molecular orbital (ELUMO = -2.766eV), were calculated to understand CMTD's reactivity. Additionally, global reactivity descriptors such as chemical hardness (η), electronegativity (χ), and the electron fraction transferred (ΔN) from CMTD to the iron surface were analyzed. These findings suggest that CMTD is highly effective in preventing corrosion and can be applied in industries where mild steel is exposed to acidic environments, such as in petrochemical and industrial cleaning processes.

Mechanistic Principles of Hydrogen Evolution in the Membrane-Bound Hydrogenase.

The membrane-bound hydrogenase (Mbh) from Pyrococcus furiosus is an archaeal member of the Complex I superfamily. It catalyzes the reduction of protons to H2 gas powered by a [NiFe] active site and transduces the free energy into proton pumping and Na+/H+ exchange across the membrane. Despite recent structural advances, the mechanistic principles of H2 catalysis and ion transport in Mbh remain elusive. Here, we probe how the redox chemistry drives the reduction of the proton to H2 and how the catalysis couples to conformational dynamics in the membrane domain of Mbh. By combining large-scale quantum chemical density functional theory (DFT) and correlated ab initio wave function methods with atomistic molecular dynamics simulations, we show that the proton transfer reactions required for the catalysis are gated by electric field effects that direct the protons by water-mediated reactions from Glu21L toward the [NiFe] site, or alternatively along the nearby His75L pathway that also becomes energetically feasible in certain reaction steps. These local proton-coupled electron transfer (PCET) reactions induce conformational changes around the active site that provide a key coupling element via conserved loop structures to the ion transport activity. We find that H2 forms in a heterolytic proton reduction step, with spin crossovers tuning the energetics along key reaction steps. On a general level, our work showcases the role of electric fields in enzyme catalysis and how these effects are employed by the [NiFe] active site of Mbh to drive PCET reactions and ion transport.

A Comparative DFT Investigation of the Adsorption of Temozolomide Anticancer Drug over Beryllium Oxide and Boron Nitride Nanocarriers.

Herein, attempts were made to explore the adsorption prospective of beryllium oxide (Be12O12) and boron nitride (B12N12) nanocarriers toward the temozolomide (TMZ) anticancer drug. A systematic investigation of the TMZ adsorption over nanocarriers was performed by using quantum chemical density functional theory (DFT). The favorability of Be12O12 and B12N12 nanocarriers toward loading TMZ was investigated through A↔D configurations. Substantial energetic features of the proposed configurations were confirmed by negative adsorption (E ads) energy values of up to -30.47 and -26.94 kcal/mol for TMZ•••Be12O12 and •••B12N12 complexes within configuration A, respectively. As per SAPT results, the dominant contribution beyond the studied adsorptions was found for the electrostatic forces (E elst = -100.21 and -63.60 kcal/mol for TMZ•••B12N12 and •••Be12O12 complexes within configuration A, respectively). As a result of TMZ adsorption, changes in the energy of molecular orbitals followed by alterations in global reactivity descriptors were observed. Various intermolecular interactions within the studied complexes were assessed by QTAIM analysis. Notably, a favorable adsorption process was also observed under the effect of water with adsorption energy ( reaching -28.05 and -22.26 kcal/mol for TMZ•••B12N12 and •••Be12O12 complexes within configuration A, respectively. The drug adsorption efficiency of the studied nanocarriers was further examined by analyzing the IR and Raman spectra. From a sustained drug delivery point of view, the release pattern of TMZ from the nanocarrier surface was investigated by recovery time calculations. Additionally, the significant role of doping by heavy atoms (i.e., MgBe11O12 and AlB11N12) on the favorability of TMZ adsorption was investigated and compared to pure analogs (i.e., Be12O12 and B12N12). The obtained data from thermodynamic calculations highlighted that the adsorption process over pure and doped nanocarriers was spontaneous and exothermic. The emerging findings provide a theoretical base for future works related to nanocarrier applications in the drug delivery process, especially for the TMZ anticancer drug.

Quantum chemical, vibrational, microhardness, thermal and antibacterial studies on polymorphic drug crystal: Sulfanilamide (β-form)

The widely known pharmaceutical drug compound, Sulfanilamide, crystallized in the β-form of its polymorphic phases by slow evaporation of the parent solution at room temperature. The single crystal X-ray diffraction study provided information about the cell parameters, confirming the β-phase of the compound. Optimization of the molecule by quantum chemical computations, viz., Hartree-Fock (HF) Theory and Density Functional Theory (DFT) using the B3LYP function with 6–311++G(d,p) basis set for both in restricted methods were carried out. The Frontier Molecular Orbital studies gave the HOMO and LUMO values, and Mulliken charge analysis showed the possible charge delocalization and donor-acceptor sites. Vibrational bands of the functional groups present in the β-Sulfanilamide compound were identified and investigated using FT-IR and FT-Raman spectroscopy in the range of 4000–400 cm−1. The grown crystal was transparent in the entire UV region with a lower cut off wavelength of 241 nm as investigated by the UV–Vis-NIR analysis. Thermogravimetric and differential thermal analyses of the compound were carried out and the results were plotted as TGA/DTA graph. Microhardness tests were used to determine the mechanical parameters of this pharmaceutical compound. Sulfanilamide, a well-known antibacterial agent and used to treat a variety of bacterial infections, was tested using the zone inhibition method and the antibacterial activity was confirmed.

Polymer Nanocomposite Based on Pyrolyzed Polyacrylonitrile Doped with Carbon Nanotubes: Synthesis, Properties, and Mechanism of Formation.

The paper investigates the possibility of fabricating a carbon nanotubes (CNT)-modified nanocomposite based on pyrolyzed polyacrylonitrile (PPAN). The layered structure of PPAN ensures the attachment of nanotubes (NT) to the polymer matrix, forming enhanced PPAN/CNT nanocomposites. We synthesized a PPAN/CNT polymer nanocomposite and investigated its mechanical, conductive, and electronic properties. Using the quantum chemical method density functional theory (DFT), we studied an interaction mechanism between PPAN and single-walled carbon nanotubes. We described the structural features and electron energy structure of the obtained systems. We found that the attachment of a CNT to the PPAN matrix increases tensile strength, electrical conductivity, and thermal stability in the complex. The obtained materials were exposed to electromagnetic radiation and the dielectric constant, reflection, transmission, and absorption coefficients were measured. The study demonstrates the possibility of using carbon nanotubes for reinforcing polyacrylonitrile polymer matrix, which can result in the development of an enhanced class of materials possessing the properties of both polymers and CNTs.

Aggregation-Induced Modulation of Ground and Excited State Photophysics of 5-(tert-Butyl)-2-Hydroxy-1,3-Isophthalaldehyde (5-tBHI).

5-(tert-Butyl)-2-hydroxy-1,3-isophthalaldehyde (5-tBHI) is a photochromic material susceptible to either excited state proton transfer or excited state intramolecular proton transfer, depending upon the solvent. However, it has also been found to aggregate in the presence of sodium dodecyl sulfate. In this current study, based on the steady-state and time-resolved spectroscopy, supported by crystallography, quantum chemical density functional theory calculation, and molecular dynamics (MD) simulation, we report on the aggregation of this potential single benzene-based emitter (SBBE) in neat solvents as well as solid phase to modulate its photophysics. It has been found that 5-tBHI forms mixed aggregates of different orders, owing to the presence of both enolic and tautomeric forms, to yield tunable emission, although the emission intensity is quenched. These findings suggest that the intramolecular hydrogen bonding of 5-tBHI not only limits intermolecular interactions but also promotes nonradiative deactivation pathways. Hence, designing and structural engineering, with a focus to suppressing intramolecular hydrogen bonding as well as increasing through space conjugation by replacing the aldehydic moieties with bulky aliphatic or aromatic ketonic groups, can be a plausible approach to yielding improved probes with tunable emission and higher fluorescence quantum yields.

Yttrium‐ and nitrogen‐doped NiCo phosphide nanosheets for high‐efficiency water electrolysis

AbstractEngineering high‐performance and low‐cost bifunctional catalysts for H2 (hydrogen evolution reaction [HER]) and O2 (oxygen evolution reaction [OER]) evolution under industrial electrocatalytic conditions remains challenging. Here, for the first time, we use the stronger electronegativity of a rare‐Earth yttrium ion (Y3+) to induce in situ NiCo‐layered double‐hydroxide nanosheets from NiCo foam (NCF) treated by a dielectric barrier discharge plasma NCF (PNCF), and then obtain nitrogen‐doped YNiCo phosphide (N‐YNiCoP/PNCF) after the phosphating process using radiofrequency plasma in nitrogen. The obtained N‐YNiCoP/PNCF has a large specific surface area, rich heterointerfaces, and an optimized electronic structure, inducing high electrocatalytic activity in HER (331 mV vs. 2000 mA cm−2) and OER (464 mV vs. 2000 mA cm−2) reactions in 1 M KOH electrolyte. X‐ray absorption spectroscopy and density functional theory quantum chemistry calculations reveal that the coordination number of CoNi decreased with the incorporation of Y atoms, which induce much shorter bonds of Ni and Co ions and promote long‐term stability of N‐YNiCoP in HER and OER under the simulated industrial conditions. Meanwhile, the CoN‐YP5 heterointerface formed by plasma N‐doping is the active center for overall water splitting. This work expands the applications of rare‐Earth elements in engineering bifunctional electrocatalysts and provides a new avenue for designing high‐performance transition‐metal‐based catalysts in the renewable energy field.

A Molecular Modeling Study into Brønsted and Lewis Acid Catalyzed Conversion of CBD into Other Cannabinoids

A Molecular Modeling Study into Brønsted and Lewis Acid Catalyzed Conversion of CBD into Other Cannabinoids

From Molecules to Devices: Insights into Electronic and Optical Properties of Pyridine-Derived Compounds Using Density Functional Theory Calculations.

In this study, we delve into the electronic structure, spectroscopic, and optical properties of five benzo derivatives of pyridine, namely, 5-(4-chlorophenyl)-2-fluoropyridine (1), 2-fluoro-5-(4-fluorophenyl)pyridine (2), 4-(2-fluoropyridin-5-yl)phenol (3), 5-(2,3-dichlorophenyl)-2-fluoropyridine (4), and 5-(5-bromo-2-methoxyphenyl)-2-fluoropyridine (5). Utilizing quantum chemical density functional theory calculations at the B3LYP and Perdew-Burke-Ernzerhof levels of theory combined with the 6-311G(d,p) and 6-311++G(d,p) basis sets, we investigated the electronic and optical characteristics of these compounds. Band structure calculations were conducted for their crystalline structures, revealing a direct band gap varying from 3.018 to 3.558 eV, with the valence band maximum and conduction band minimum located at the G point in the Brillouin zone. The optical properties were analyzed, including the dielectric functions, reflectivity, and refractive index. Notably, reflectivity was found to be minimal in the photon energy range of 0.0-3.0 eV, and the static refractive index, n(0), ranged from 1.55 to 1.70. The research also involved assessing the reactivity of the compounds through calculation of the frontier orbital energy gaps (ΔE), indicating a significant charge transfer and high reactivity. Additionally, we performed frequency analysis to unveil the Fourier-transform infrared spectra of compounds 1-5 at room temperature. Molecular electrostatic potential surfaces of the optimized structures were employed to map the electrophilic and nucleophilic regions of the compounds. This investigation provides a comprehensive understanding of the electronic and optical properties of these pyridine derivatives, shedding light on their potential applications in optoelectronics.

Mechanism of a novel metal-free carbonic anhydrase.

The recently discovered metal-free carbonic anhydrase (CA) enzyme may significantly impact the global carbon dioxide (CO2) cycle, as it can irreversibly perform the CO2 hydration reaction. In this study, we investigated several key aspects of metal-free CA, including the identification of the catalytic site, the determination of the CO2 binding site, and the mechanism of catalysis. This is achieved through classical molecular dynamics (MD) simulations, quantum chemical density functional theory (DFT), and hybrid quantum mechanics/molecular mechanics (QM/MM) calculations. Our study indicates that the experimental structure based on X-ray crystallography, which shows the 'bicarbonate (HCO3-) product' trapped in the hydrophilic region of metal-free CA, might not accurately depict the actual enzyme-substrate interaction. Instead, the simulation reveals that CO2 prefers the hydrophobic zone, which serves as the primary catalytic site. It also highlights the strategic role of a gatekeeper residue (Phe504), which assists in regulating the transportation of CO2 by tilting its aromatic plane. Additionally, the hybrid QM/MM calculations establish that CO2 hydration is catalyzed within the hydrophobic zone by a deprotonated tyrosine with the help of an organized water chain.

Atomistic modelling and NMR studies reveal that gallium can target the ferric PQS uptake system in P. aeruginosa biofilms.

Intravenous gallium nitrate therapy is a novel therapeutic strategy deployed to combat chronic Pseudomonas aeruginosa biofilm infections in the lungs of cystic fibrosis (CF) patients by interfering with iron (Fe3+) uptake. The therapy is a source of Ga3+, which competes with Fe3+ for siderophore binding, subsequently disrupting iron metabolism and inhibiting biofilm proliferation in vivo. It was recently demonstrated that the Pseudomonas quinolone signal (PQS) can chelate Fe3+ to assist in bacterial iron uptake. However, it is unknown whether exogenous gallium also targets [Fe(PQS)3] uptake, which, in turn, would extend the mechanism of gallium therapy beyond siderophore competition, potentially supporting use of the therapy against P. aeruginosa mutants deficient in siderophore uptake proteins. To that end, the thermodynamic feasibility of iron-for-gallium cation exchange into [Fe(PQS)3] was evaluated using quantum chemical density functional theory (DFT) modelling and verified experimentally using 1H nuclear magnetic resonance (NMR). We demonstrate here that Ga3+ can strongly bind to three PQS molecules and, furthermore, displace and substitute Fe3+ from the native chelate pocket within PQS complexes, through a Trojan horse mechanism, retaining the key structural features present within the native ferric complex. As such, [Fe(PQS)3] complexes, in addition to ferric-siderophore complexes, represent another target for gallium therapy.

Predicting 51V nuclear magnetic resonance observables in molecular crystals.

Solid-state nuclear magnetic resonance (NMR) spectroscopy and quantum chemical density functional theory (DFT) calculations are widely used to characterize vanadium centers in biological and pharmaceutically relevant compounds. Several techniques have been recently developed to improve the accuracy of predicted NMR parameters obtained from DFT. Fragment-based and planewave-corrected methods employing hybrid density functionals are particularly effective tools for solid-state applications. A recent benchmark study involving molecular crystal compounds found that fragment-based NMR calculations using hybrid density functionals improve the accuracy of predicted 51V chemical shieldings by 20% relative to traditional planewave methods. This work extends the previous study, including a careful analysis of 51V chemical shift anisotropy, electric field gradient calculations, and a more extensive test set. The accuracy of planewave-corrected techniques and recently developed fragment-based methods using electrostatic embedding based on the polarized continuum model (PCM) are found to be highly competitive with previous methods. Planewave-corrected methods achieve a 34% improvement in the errors of predicted 51V chemical shieldings relative to planewave. Additionally, planewave-corrected and fragment-based calculations were performed using PCM embedding, improving the accuracy of predicted 51V chemical shielding (CS) tensor principal values by 30% and values by 15% relative to traditional planewave methods. The performance of these methods is further examined using a redox-active oxovandium complex and a common 51V NMR reference compound.

Synergistic Effect of Composite Complex Agent on BTA Removal in Post-Cu-CMP: Experimental and Theoretical Analysis

Nowadays the development of nanoscale-interconnected integrated circuit chips makes the chemical mechanical polishing (CMP) and post-CMP cleaning more challenging. In general, organic residues such as benzotriazole (BTA) can adsorb on the wafer surface after CMP process and form thin films to prevent the contact between cleaning solution and the wafer surface, which thus can seriously affect the post-CMP cleaning process. And the efficient removal of BTA remains problematic due to the potential introduction of additional impurities. Therefore, a new alkaline cleaning solution based on citric acid (CA) was proposed to improve the removal efficiency of BTA. Results exhibit that the cleaning efficiency of BTA residues can reach 98.86% with 400 ppm tetraethyl ammonium hydroxide (TEAH) and 0.6 wt% CA (pH = 10.5). X-ray photoelectron spectroscopy (XPS) measurements show that the cleaning solution can coordinate with copper ions to break the ionization balance of Cu-BTA. In addition, the electronic properties and reaction sites on copper surface were determined by quantum chemical calculation and density functional theory (DFT). The theoretical analysis indicates that CA has hydroxyl and carboxyl functional groups, and its presence with TEAH can promote the complexation of Cu ions, which accelerates the breakage of Cu-BTA and the desorption of BTA from the copper surface.

New benzisoxazole derivative: A potential corrosion inhibitor for mild steel in 0.5 M hydrochloric acid medium -insights from electrochemical and density functional theory studies

6-fluoro-3-(4-piperidinyl)-1,2-benzisoxazole. HCl (FPBH), a substituted benzisoxazole derivative, was prepared from isonipecotic acid and characterized using various spectroscopic techniques. Using electrochemical examinations such as potentiodynamic polarisation (PDP) and electrochemical impedance spectroscopic (EIS) technique, the corrosion mitigation capabilities of this compound for mild steel (MS) in 0.5 M HCl medium were investigated. Theoretical studies were performed using quantum chemical calculations and density functional theory (DFT). PDP results exhibited the mixed-type behavior of FPBH and showed a maximum efficiency of 94.5 % at 1 × 10−3 M. The development of a protective adsorbed layer of FPBH decreases the corrosion current density (icorr) and corrosion rate (CR). The EIS technique revealed that the rise in the charge transfer resistance (Rct) values and reduction in the thickness of the double-layer capacitance (Cdl) reflected the drop in corrosion rate. The adsorption of FPBH took place through physisorption by conforming Langmuir's isotherm. The DFT method was performed on the optimized structure of FPBH to get additional evidence on the action mode of FPBH with the metal surface.

Structural, spectroscopic properties ant prospective application of a new nitropyridine amino N-oxide derivative: 2-[(4-nitropyridine-3-yl)amino]ethan-1-ol N-oxide

A new nitropyridine amino N-oxide derivative 2-[(4-nitropyridine-3-yl)amino]ethan-1-ol N-oxide was synthesized and its structural and optical properties were described. Its structure obtained from the X-ray diffraction (XRD) studies was related to the Infrared spectroscopy (IR), Raman spectroscopy (RS), electron Ultraviolet–Visible spectroscopy (UV–VIS) and emission spectra measurements. The experimental results were analyzed in terms of theoretical data obtained from quantum chemical Density Functional Theory (DFT) and Natural Bond Orbital (NBO) calculations. The 6-311G(2d,2p) basis set with the B3LYP functional was used to discuss its optimized structure and vibrational properties. Femtosecond excitation was used to recognize the depopulation mechanism of the electron excited states in the studied compound. It was found that the intermolecular interactions strongly influence the physicochemical properties and application of the new nitropyridine amino N-oxide derivative.

Investigating the mechanism behind the synergistic ultraviolet photooxidation degradation of gaseous benzene through modified ACF

The effects of relative humidity were studied on the direct conversion efficiency, mineralization rate and components of waste gas from benzene photooxidation degradation. The adsorption energies, adsorption types, and molecular interaction forces of activated carbon fiber (ACF) modified with nitrogen and oxygen-containing functional groups were calculated using quantum chemical density functional theory (DFT) calculations and wave function analysis. Five polar intermediate products including acetone, acetol, hexanal, benzaldehyde, and acetophenone generated from benzene photooxidation degradation were selected as the computational object. The independent gradient model method based on Hirshfeld partition was used to study the weak interactions among the five equilibrium molecular adsorption configurations. The results demonstrated that the direct conversion efficiency of benzene increased first and then decreased with increasing relative humidity. The maximum direct conversion efficiency was 82% observed at a relative humidity of 50%. The mineralization rate decreased significantly at higher relative humidity, and the lowest value was 2%. The overall adsorption effect of nitrogen-containing functional groups on the modified ACF surface is higher than that of oxygen-containing functional groups. The functional groups with the best adsorption effect are ACF modified by pyridone, amino and carboxyl groups. Combined with electron localization function (ELF) analysis and Mayer bond-level calculation, it was found that all the modified ACF surfaces do not form chemical bonds for the equilibrium molecular adsorption configurations of the five organic compounds, which belong to physical adsorption. The adsorption of five intermediate products by modified ACF mainly depended on hydrogen bonds or van der Waals forces. The existence of hydrogen bonds greatly improved the adsorption capacity of modified ACF to organic molecules.

Role of Steric Effects on Rates of Hydrogen Atom Transfer Reactions.

The influence of steric effects on the rates of hydrogen atom transfer (HAT) reactions between oxyradicals and alkanes is explored computationally. Quantum chemical density functional theory computations of transition states show that activation barriers and reaction enthalpies are both influenced by bulky substituents on the radical but very little by substituents on the alkane. The activation barriers remain roughly correlated with reaction enthalpies via the Evans-Polanyi relationship even when steric repulsion effects become important, although dispersion effects sometimes stabilize transition states. By making comparisons to previously developed Evans-Polanyi and modified Roberts-Steel relationships, we find that HAT reactions between bulky molecules remain well-described by these relationships.