Quantum Mechanical Approach Research Articles

Molecular saturation determines distinct plasmonic enhancement scenarios for two-photon absorption signal

Two-photon absorption in molecules, of significance for high-resolution imaging applications, is typically characterised with low cross sections. To enhance the TPA signal, one effective approach exploits plasmonic enhancement. For this method to be efficient, it must meet several criteria, including broadband operational capability and a high fluorescence rate to ensure effective signal detection. In this context, we introduce a plus-shaped silver nanostructure designed to exploit the coupling of bright and dark plasmonic modes. This configuration considerably improves both the absorption and fluorescence of molecules across near-infrared and visible spectra. By fine-tuning the geometrical parameters of the nanostructure, we align the plasmonic resonances with the optical properties of specific TPA-active dyes, i.e., ATTO 700, Rhodamine 6G, and ATTO 610. The expected TPA signal enhancement is evaluated using classical estimations based on the assumption of independent enhancement of absorption and fluorescence. These results are then compared with outcomes obtained in a quantum-mechanical approach to evaluate the stationary photon emission rate. Our findings reveal the important role of molecular saturation determining the regimes where either absorption or fluorescence enhancement leads to an improved TPA signal intensity, considerably below the classical predictions. The proposed nanostructure design not only addresses these findings, but also might serve for their experimental verification, allowing for active polarization tuning of the plasmonic response targeting the absorption, fluorescence, or both. The insight into quantum-mechanical mechanisms of plasmonic signal enhancement provided in our work is a step forward in the more effective control of light-matter interactions at the nanoscale.

Reliable Diradical Characterization via Precise Singlet-Triplet Gap Calculations: Application to Thiele, Chichibabin, and Müller Analogous Diradicals.

Accurately calculating the diradical character (y0) of molecular systems remains a significant challenge due to the scarcity of experimental data and the inherent multireference nature of the electronic structure. In this study, various quantum mechanical approaches, including broken symmetry density functional theory (BS-DFT), spin-flip time-dependent density functional theory (SF-TDDFT), mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT), complete active space self-consistent field (CASSCF), complete active space second-order perturbation theory (CASPT2), and multiconfigurational pair-density functional theory (MCPDFT), are employed to compute the singlet-triplet energy gaps (EST) and y0 values in Thiele, Chichibabin, and Müller analogous diradicals. By systematically comparing the results from these computational methods, we identify optimally tuned long-range corrected functional CAM-B3LYP in the BS-DFT framework as a most efficient method for accurately and affordably predicting both EST and y0 values. Additionally, our results demonstrate that (i) MRSF-TDDFT performs much better than SF-TDDFT; (ii) the MCPDFT method is robust in determining EST with minimal dependence on the choice of active space. These findings provide insight into the electronic structure and diradical character of the investigated molecules and highlight effective computational strategies for future studies in this domain. Thus, this work not only advances our understanding of diradical systems but also offers practical guidelines for their computational investigation.

Computational study on novel RhCpX (X = CF3, SiF3, CCl3, SO3H) as promising catalysts in the [3 + 2] azide-alkyne cycloaddition reaction: insights into mechanistic pathways and reactivity.

This computational study investigated the catalytic efficiency of novel RhCpX complexes (X = CF3, SiF3, CCl3, SO3H) in [3 + 2] azide-alkyne cycloaddition reactions via density functional theory (MN12-L/Def2-SVP). Through quantum mechanical approaches, we explore the impact of different substituents on the Cp* ligand on the mechanism, selectivity, and reactivity of these Rh-based catalysts. Non-covalent interaction (NCI) and reduced density gradient (RDG) analyses, along with frontier molecular orbital (FMO) and Hirshfeld atomic charge analyses, were utilized to assess ligand stability and catalytic performance. The results show that RhCpSO3H offers the highest stability and reactivity, favoring the formation of 1,5-disubstituted triazoles. Our findings highlight the potential of these novel RhCpX complexes as effective catalysts in synthetic and pharmaceutical applications.

Hamiltonian for complex plasmas

The Hamiltonian for a complex plasma involving dust spinning motion in a magnetic field is proposed. The formulation is in a classical limit of a quantum mechanical approach based on the Dirac equation, a relativistic wave equation in which the spin of particles is considered. The quantum mechanical spin term –γs·B [γ=gq/2m, g=2(Lande´ g−factor),q is a charge, m is a mass of a particle, and s = spin operator] is replaced by –γs·B [γ with g=1, s = I(ω+γB), I is the moment of inertia of a dust particle, and ω is the spinning angular velocity of a dust particle] in a classical limit. The wave–particle interaction involving spin motion is described as an interaction between particles and quasiparticles by the second quantization. The equation of motion with a damping term shows the relaxation of spinning dust particles aligning with the magnetic field.

Mutual Neutralization in Collisions of Li+ with O−

The total and differential cross-sections and final state distribution for mutual neutralization in collisions of Li+ with O− were calculated using an ab initio quantum mechanical approach based on potential energy curves and non-adiabatic coupling elements computed with the multi-reference configuration interaction method. The final state distributions favored channels with excited oxygen states, indicating a strong effect of electron correlation, and the electron transfer could not be described by a simple one-electron exchange process.

Deciphering the Instability of the Black Hole Ringdown Quasinormal Spectrum.

The spectrum of the quasinormal modes of the gravitational waves emitted during the ringdown phase following the merger of two black holes is of primary importance in gravitational astronomy. However, the spectrum is extremely sensitive to small disturbances of the system, thus potentially jeopardizing the predictions of the gravitational-wave observables. We offer an analytical and intuitive explanation of such an instability and its properties based on the transfer matrix approach of quantum mechanics. We also give a simple interpretation of the fact that the prompt ringdown response in the time domain and the black hole greybody factor receive parametrically small corrections, thus being robust observables.

Dispersion-corrected DFT calculations and dynamic molecular simulations to investigate conformational stability of Lidocaine towards β-CD and HP-β-CD

Lidocaine (LDC) is one of the most important local anaesthesia compounds (LAs), designated to treat acute and chronic pain, especially in clinical applications. In the purpose to improve its lower solubility and bioavailability, numerous researches have been conducted to study the exact mode of association between the LDC molecule and cyclodextrins as drug carriers. Although, the reported structural details on LDC/β-CD and LDC/HP-β-CD inclusion complexes remain largely unexplored. The LDC molecule presents different spatial arrangements inside the hydrophobic cavities of the above-mentioned hosts; either the phenyl moiety or the diethylamino part is totally inserted. Hence, in the present work, we attempt to deepen our understanding about conformational preferences on the binding modes of LDC by investigating the quantum mechanical approach results.The PM3 method combined with the pure corrected functional B97D3 revealed the tendency of LDC to enter its diethylamino inside the host, leaving the rest of molecule externally, and consequently form an inclusion complex with HP-β-CD more stable than with the native β-CD by approximately 12 kcal mol−1.The probability of partial insertion of LDC is further ascertained by MD simulations investigation running for 500 ns. The trajectory analysis of MD process showed that the diethyl amino fragment is accommodated inside the HP-β-CD's cavity for a significant period (82 % of the simulation time), while it is estimated to be 78 % in the case of LDC/β-CD complex.Moreover, the wave function analysis, based on QTAIM, Reduced Density Gradient (RDG) and 2D Fingerprint, illustrated NCIs interactions and sustained the contribution of numerous van der Waals forces and weaker H-bonds interactions in the stability of studied ICs.

Quantum mechanical approaches and molecular docking studies of platinum based anticancer drugs Satraplatin and picoplatin structures

The structures of the anticancer drug compounds satraplatin and picoplatin are optimized, and theoretical studies done by Density Functional Theory (DFT) to investigate the optical properties, global chemical descriptors, and band gap were calculated using the obtained Frontier molecular orbital values. The theoretically obtained data of the platinum drugs found to possess low energy gap values and low chemical hardness with high chemical softness describe that the compounds are chemically stable and most reactive. Using the molecular docking process, the binding mechanisms of the satraplatin and picoplatin drugs with cancer DNA structures were studied, and the results were analyzed. For the two drug compounds examined, satraplatin has shown the least binding energies at −5.06kcal/mol compared to picoplatin at −2.69 kcal/mol, and conformations with root mean square deviation (RMSD) values by DNA structures are less than or equal to 2.00 Å in targeting the specific DNA target residues of the reference bound ligand. The grid box was generated using the selective grid parameters using the Autodock 4.2 program. The drug molecules found to have the least binding energy value with the lowest inhibition constant implicate the good docking score towards the DNA structure by the docking studies. DFT studies also show good structural properties and chemical reactivity. From the obtained results, satraplatin and picoplatin were found to have good chemical descriptors and good binding affinity and are best suited for biological molecular targets.

Unsupervised representation learning of Kohn–Sham states and consequences for downstream predictions of many-body effects

Representation learning for the electronic structure problem is a major challenge of machine learning in computational condensed matter and materials physics. Within quantum mechanical first principles approaches, density functional theory (DFT) is the preeminent tool for understanding electronic structure, and the high-dimensional DFT wavefunctions serve as building blocks for downstream calculations of correlated many-body excitations and related physical observables. Here, we use variational autoencoders (VAE) for the unsupervised learning of DFT wavefunctions and show that these wavefunctions lie in a low-dimensional manifold within latent space. Our model autonomously determines the optimal representation of the electronic structure, avoiding limitations due to manual feature engineering. To demonstrate the utility of the latent space representation of the DFT wavefunction, we use it for the supervised training of neural networks (NN) for downstream prediction of quasiparticle bandstructures within the GW formalism. The GW prediction achieves a low error of 0.11 eV for a combined test set of two-dimensional metals and semiconductors, suggesting that the latent space representation captures key physical information from the original data. Finally, we explore the generative ability and interpretability of the VAE representation.

Quantum Effects Induced by Defects in Thin-Film Structures: A Hybrid Modeling Approach to Conductance and Transmission Analysis

This study investigated the possibility of quantum effects arising from defects resulting from the use of textronic electroconductive thin films and evaluated their impact on control characteristics. A hybrid model, where the classical approach to determine stationary fields based on the boundary element method was combined with a quantum mechanical approach using nonequilibrium Green’s functions, was created. The results of conductance and transmission coefficient simulations for different types of defects in the studied structure and a wide range of temperatures assuming two different control modes are presented. Based on the results, the conditions for the occurrence of quantum effects on the surface of conducting paths containing defects were specified, and their impact on conductance in the quantum mechanical approach was estimated.

Elucidating the E‐Cadherin⋯ADTC5 Interactions: A Theoretical Examination of Amino Acid Active Site Binding on the Electronic Level via Density Functional Theory

AbstractThe presence of E‐cadherin⋯E‐cadherin interactions in the intercellular space (paracellular pathway) poses a notable limitation in drug delivery across the blood‐brain barrier (BBB). ADTC5 peptide has shown promising results in improving drug delivery across the BBB by modulating E‐cadherin⋯E‐cadherin interactions. However, the study of E‐cadherin⋯ADTC5 amino acid interactions using quantum mechanics approach has not been observed clearly. Herein, we observed the interaction between E‐cadherin⋯ADTC5 amino acids using density functional theory (DFT). Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), and reduced density gradient (RDG) analysis are performed to study the non‐covalent interaction in detail. The Arg55⋯Asp2 shows the strongest interaction between E‐cadherin⋯ADTC5 modulation, indicated by the highest stabilization energy (E(2)), and hydrogen bonding energy (EHB) about 22.04 and −6.90 kcal/mol, respectively. This interaction is dominated by hydrogen bonding. Such advancements could lead to significant improvements in therapeutic strategies for neurodegenerative diseases, where effective drug delivery across the BBB remains a major challenge.

Determination of the particle size distribution of cube-shaped colloidal perovskite quantum dots from photoluminescence spectra: A combined theoretical-experimental approach.

A theoretical-experimental approach is proposed to convert the photoluminescence spectra of colloidal perovskite quantum dot ensembles into accurate estimates for their intrinsic particle size distribution functions. Two main problems were addressed and properly correlated: the size dependence of the first excitonic transition in a single cube-shaped quantum dot and the inhomogeneous broadening of the fluorescence line shape due to the size nonuniformity of the chemically prepared quantum dot suspension in addition to the single-dot homogeneous broadening. By applying the reported methodology to CsPbBr3 quantum dot samples belonging to the strong and intermediate confinement regimes, the calculated size distributions exhibited close agreement with those obtained from transmission electron microscopy, with precise estimates for the average particle size and standard deviation. Specifically for strongly confined ultrasmall CsPbBr3 quantum dots, the presented spectroscopic model for size distribution computation is based on a new analytical expression for the size-dependent bandgap, which was developed within the framework of the finite-depth square-well effective mass approximation accounting for band nonparabolicity effects. Such a quantum mechanical approach correctly predicts the expected transition to the intermediate confinement regime in sufficiently large quantum dots, which are traditionally described by the well-known bandgap equation in the infinite potential barrier limit with a spatially correlated electron-hole wavefunction and nonparabolic carrier effective masses. The proposed calculation scheme originates from general theoretical considerations so that it can be readily adapted to semiconductor quantum dots of many other systems, from all inorganic metal halides to hybrid perovskite materials, regardless of the adopted chemical synthesis route.

A Quantum Mechanical Approach to The Mechanism of Asymmetric Synthesis of Chiral Amine by Imine Reductase from Stackebrandtia Nassauensis.

The asymmetric synthesis of tetrahydroisoquinolines (THIQs) has gained importance in recent years due to their significant potential in drug development studies. In this study, the conversion of 1-methyl-3,4-dihydroisoquinoline substrate to a chiral amine, 1-methyl-1,2,3,4-tetrahydroisoquinoline, under the catalysis of the stereoselective imine reductase enzyme from Stackebrandtia nassauensis (SnIR) was investigated in detail to elucidate the mechanism and explain the experimental enantioselectivity. The results were found to be in agreement with the experimental data. To elucidate the reaction mechanism, quantum mechanical calculations were performed by considering a large cluster of the active site of the enzyme. In this regard, possible reaction pathways leading to both R- and S-products with the corresponding intermediates and the transition states for the hydride transfer from the cofactor to the substrate were considered by density functional theory (DFT) calculations, and the factors contributing to the observed stereoselectivity were sought. The calculations supported a stepwise mechanism rather than the concerted protonation and the hydride transfer steps. The stereoselectivity in the hydride transfer was found to be due not only to the stability of the enzyme-subtrate complex but also to the corresponding reaction barriers. The calculations were performed at the wB97XD/6-311+G(2df,2p)//B3LYP/6-31G(d,p) level of theory using the PCM approach.

Novel, soluble 3-heteroaryl-substituted tanshinone mimics attenuate the inflammatory response in murine macrophages

The RNA binding protein Human Antigen R (HuR) has been identified as a main regulator of the innate immune response and its inhibition can lead to beneficial anti-inflammatory effects. To this aim, we previously synthesized a novel class of small molecules named Tanshinone Mimics (TMs) able to interfere with HuR-RNA binding, and that dampen the LPS-induced immune response. Herein, we present a novel series of TMs, encompassing thiophene 3/TM9 and 4/TM10, furan 5/TM11 and 6/TM12, pyrrole 7b/TM13, and pyrazole 8. The furan-containing 5(TM11) showed the greatest inhibitory effect of the series on HuR-RNA complex formation, as suggested by RNA Electromobility Shift Assay and Time-Resolved FRET. Molecular Dynamics Calculation of HuR − 5/TM11 interaction, quantum mechanics approaches and Surface Plasmon Resonance data, all indicates that, within the novel heteroaryl substituents, the furan ring better recapitulates the chemical features of the RNA bound to HuR. Compound 5/TM11 also showed improved aqueous solubility compared to previously reported TMs. Real-time monitoring of cell growth and flow cytometry analyses showed that 5/TM11 preferentially reduced cell proliferation rather than apoptosis in murine macrophages at immunomodulatory doses. We observed its effects on the innate immune response triggered by lipopolysaccharide (LPS) in macrophages, showing that 5/TM11 significantly reduced the expression of proinflammatory cytokines as Cxcl10 and Il1b.

Incrimination and impact on recovery times and effects of BN nanostructures on antineoplastic drug-electronic density study.

By delivering the drug to the intended cell location, the use of nanomaterials in the drug delivery system may influence how the patient receives the medication and may assist in mitigating severe side effects. Density functional theory was used to assess the use of boron carbon nitride nanocages (BNCNCs), boron nitride (BNNSs), and boron carbon nitride nanosheets (BNCNSs) as melphalan (Mln) drug carriers in both the gaseous and fluid phases. We systematically examined the dipole moment, density of states, frontier molecular orbital, and optimal adsorption energy to understand the targeted drug delivery potential of these nanostructures. Adsorption energy analysis revealed that in both gas and water media, Mln drug adsorption takes place spontaneously on all the conjugated structures. The occurrence of adsorption energy as physisorbed energy suggests that the process is reversible, and desorption can take place with a much lower energy input. This physical contact is appropriate for the unquestionable unloading of Mln medications to the intended location. The reactivity is higher in BNNSs and BNCNSs, while the stability is higher in BNCNCs. The recovery time shows a shorter time for BNNSs and BNCNSs, while BNCNC shows a potential desorption time in higher temperature. These conclusions are corroborated by the results of the quantum theory of atoms in molecules (QTAIM). After the interaction analysis, it was observed that the BNCNCs can act as potential carriers for the melphalan. From dipole moment analysis, all three nanostructures show a high hydrophilic nature but quite higher in BNCNCs after doping in both media. Overall, all the structures show the potential carrier for melphalan drug. The quantum mechanical approach, or DFT, has been used to study the fundamental structural, electrical, thermodynamic, and other aspects of proposed structures to develop an acceptable Mln drug detector. The adsorbate and all adsorbents were optimized via the hybrid B3LYP functional and the 6-311G + + (2d, p) basis set approach prior to the adsorption process. The Gaussian 09 package was used at 298K as the constant temperature and 1 atm as the constant pressure. The structures are examined using the same functional models for solvation analysis-6-311 G + + (2d, p) and B3LYP-as well as the polarized continuum model (PCM) model as the foundation set. Density of states was studied using GaussSum 3.0 software. The interaction studies QTAIM and RDG were studied using VMD and Multiwfn software.

Metallicious: Automated Force-Field Parameterization of Covalently Bound Metals for Supramolecular Structures.

Metal ions play a central, functional, and structural role in many molecular structures, from small catalysts to metal-organic frameworks (MOFs) and proteins. Computational studies of these systems typically employ classical or quantum mechanical approaches or a combination of both. Among classical models, only the covalent metal model reproduces both geometries and charge transfer effects but requires time-consuming parameterization, especially for supramolecular systems containing repetitive units. To streamline this process, we introduce metallicious, a Python tool designed for efficient force-field parameterization of supramolecular structures. Metallicious has been tested on diverse systems including supramolecular cages, knots, and MOFs. Our benchmarks demonstrate that parameters accurately reproduce the reference properties obtained from quantum calculations and crystal structures. Molecular dynamics simulations of the generated structures consistently yield stable simulations in explicit solvent, in contrast to similar simulations performed with nonbonded and cationic dummy models. Overall, metallicious facilitates the atomistic modeling of supramolecular systems, key for understanding their dynamic properties and host-guest interactions. The tool is freely available on GitHub (https://github.com/duartegroup/metallicious).

Single‐molecule methods, activation‐induced cytidine deaminase, and quantum mechanical approach to explore and prevent carcinogenesis

AbstractRecent advancements in single‐molecule methods have not only made it possible to obtain precise measurements for complex biological processes but also to produce simple mathematical models for intricate biochemical mechanisms, which would otherwise be speculative. These developments have strengthened our ability to respond through mathematical modeling to concepts of protein‒protein and protein‒DNA interactions on a nanometer level and address‐related questions. In this article, we examine an intriguing biological phenomenon in which a protein and an enzyme co‐jointly encounter carcinogenic adducts during transcription. We are focusing mainly on the dysregulation of the protein involved and the possible consequences that may arise. By providing a quantum mechanical model, we have demonstrated that the presence of carcinogenic adducts in a transcriptional bubble deregulates the protein that could cause lethal mutations. Next, we present a case study to explore carcinogenesis by suggesting an alternative experimental design. Our quantum mechanical model emphasizes the use of a quantized energies approach for specific mechanisms within the living cells. Radiation‐induced carcinogenicity can be prevented if radiation interacting with tissue is not given the energies that satisfy the quantization conditions.

Analytical estimate of effective charge and ground-state energies of two to five electron sequences up to atomic number 20 utilizing the variational method

BackgroundThe variational method, a quantum mechanical approach, estimates effective charge distributions and ground-state energy by minimizing the Hamiltonian's expectation value using trial wave functions with adjustable parameters. This method provides valuable insights into system behavior and is widely used in theoretical chemistry and physics. This paper aims to investigate ground-state energies and isoelectronic sequences using the variational method, introducing a novel approach for analyzing multi-electron systems. This technique allows for determining effective charge values and ground-state energies for 2–5 electrons sequence up to Z ≤ 20. Hydrogenic wave functions are used as a trial wave function to calculate effective charge in 1 s, 2 s, and 2p states. Two varying parameters were used to calculate an approximate wave function for the system. These values are then used in non-relativistic Hamiltonian with electron–electron interaction terms to calculate the ground-state energy of an atom.ResultThe results align with the reported experimental values, showing a marginal 1% error.ConclusionA Python algorithm is established based on the variational principle. It was found that, based on a few selected parameters in scripting the program, a very promising result was obtained. Furthermore, adding more variational parameters can minimize the difference between experimental and theoretical values, and this technique can be extended to elements with higher atomic numbers.

Tailoring Diversified Peripheral Anchor Groups in Spirofluorene‐Dithiolane‐Based Hole Transporting Materials for Efficient Organic and Perovskite Solar Cells from First‐Principle

AbstractThis quantum mechanical approach recommends push–pull molecular engineering to fabricate hole‐transporting materials (HTMs) for photovoltaic cells. It integrates acceptor moieties via thiophene to fluorene core, resulting in five novel HTMs (SFD‐1 to SFD‐5). The results exhibit that derivative HTMs show excellent coherence in excitation, dispersion, and transportation of charge carriers, ensuring robust hole mobility. The anchor moieties functionalized HTMs unveil excellent band alignment with perovskite with fitting HOMO energy levels (−4.93–−5.35 eV), less optical absorption in visible portion ( < 520). This acceptor integration has improved the hole mobility in derivatives, accredited to the smaller hole reorganization energy (0.14–0.68 eV), and greater hole transfer integral (0.22–0.33 eV). The transition density matrix analysis exhibited robust electronic coupling, subtler charge carrier overlapping and greater charge transfer length (7.48–13.73 Å). This resulted in an excellent upsurge in intrinsic charge transference (70.75–92.70%) and smaller exciton binding energy, leading to easier exciton dissociation, and fewer recombination fatalities. However, an adequate variation in dipole moment (4.04 D to 16.34 D) and Gibbs solvation‐free energy (−18.06 to −21.89 kcal mol−1) ensures facile film formation and processability. In conclusion, this approach recommends these flourene‐based HTMs are highly desireable for forthcoming solar cell technology.

‘Turn On’ fluorescent imine linked 1,2,3-triazole based chemosensor for detection of mercuric ions

The exorbitant use or erroneous management of metal ions has been incurred with catastrophic pollution of our ecological system, particularly in soil and water bodies, resulting in significant repercussions. Hence, precise identification and analysis of heavy-metal ions in intricate hydrological environments is imperative. Therefore, an imine conjugated 1,2,3-triazole derivative VPT was synthesized, characterized via FTIR, NMR (1H &13C), LCMS spectroscopic techniques and was employed for the exclusive identification of Hg2+ ions in the presence of various other metal ions via UV–Visible and fluorescence spectroscopy. The sensor VPT exhibited binding constant (Ka) value of 2.93 × 104 M−1 and detection limit value of 0.5 × 10−9 M in the ACN:H2O::4:1 medium. The stoichiometric ratio was determined using Job’s plot, which revealed a (1:1) ratio of VPT with Hg2+ ions. In addition, time-dependent, temperature-dependent, and pH titration studies were conducted via U.V-Visible spectroscopy to expand the sensor’s applicability. The viable configurations of probe VPT and its 1:1 stoichiometric with Hg2+ ion were optimized using the B3LYP/6-311G++(d,p)/LANL2DZ levels of theory in the Gaussian 09 program respectively and this semi-empirical quantum mechanics approach demonstrated a reduction in the energy gap confirming the stable formation of [VPT-Hg2+] complex. These insights facilitate the design offluorescent probe VPT for detecting Hg2+ in both environmental and biological context.