Electronic Excitation Energy Research Articles

Quantum chemical calculations and molecular docking studies of 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile

Abstract The five-membered heterocycle pyrazole has two nitrogen atoms next to each other. Natural items and pharmaceuticals using pyrazole as the nucleus have demonstrated a wide range of biological activity. Medications with pyrazole cores may have better pharmacokinetics and pharmacological effects than medicines with similar heterocyclic rings. This is because the pyrazole core has unique physicochemical properties. In this study, 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile is synthesized and characterized by means of spectrum and quantum chemical techniques. Using UV–vis absorption technique, Fourier transform infrared (FT-IR), and Fourier transform Raman (FT-Raman) techniques, the spectroscopic properties were examined. There were two regions visible in the experimental Raman as well as infrared spectra: 4,000–400 cm−1 along with 4,000–100 cm−1. The ideal molecular shape, vibrational frequencies, infrared intensity levels, and scattering from Raman were all assessed using density functional theory. The 13C (carbon) and 1H (proton) chemical shifts of the molecule were determined using nuclear magnetic resonance (NMR). The TD-DFT scheme was utilized to figure out speculative ultraviolet values and compare them to oscillator strength, electron excitation energies, and spectrum data from experiments. It is evident from the predicted HOMO-LUMO band separation energies that the transmission of charge takes place within a molecule’s structure. The chemical reactivity of the molecule has been calculated along with other global descriptive properties. Scientists investigated how charges move and the density of electrons inside a molecule using NBO analysis of the chemical they were studying. After examining the molecular electrostatic potential (MEP), a 3D picture was created that shows the compound’s nucleophilic and electrophilic areas. In addition to meeting all pertinent pharmacokinetic requirements, 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile is also readily absorbed by the gastrointestinal system. Additionally, the chemical that was synthesized had a positive interaction with the target proteins of treatments for viruses, asthma, and heart failure, as shown by molecular docking.

A procedure for the visualization of fingerprint traces on standard and thermal paper using the electron excitation energy of 1,8-diazafluoren-9-one aggregates in a polyvinylpyrrolidone polymer

A procedure for the visualization of fingerprint traces on standard and thermal paper using the electron excitation energy of 1,8-diazafluoren-9-one aggregates in a polyvinylpyrrolidone polymer

Rank-Reduced Equation-of-Motion Coupled Cluster Triples: an Accurate and Affordable Way of Calculating Electronic Excitation Energies.

In the present work, we report an implementation of the rank-reduced equation-of-motion coupled cluster method with approximate triple excitations (RR-EOM-CC3). The proposed variant relies on tensor decomposition techniques in order to alleviate the high cost of computing and manipulating the triply excited amplitudes. In the RR-EOM-CC3 method, both ground-state and excited-state triple-excitation amplitudes are compressed according to the Tucker-3 format. This enables factorization of the working equations such that the formal scaling of the method is reduced to N6, where N is the system size. An additional advantage of our method is the fact that the accuracy can be strictly controlled by proper choice of two parameters defining sizes of triple-excitation subspaces in the Tucker decomposition for the ground and excited states. Optimal strategies of selecting these parameters are discussed. The developed method has been tested in a series of calculations of electronic excitation energies and compared to its canonical EOM-CC3 counterpart. Errors several times smaller than the inherent error of the canonical EOM-CC3 method (in comparison to FCI) are straightforward to achieve. This conclusion holds both for valence states dominated by single excitations and for states with pronounced doubly excited character. Taking advantage of the decreased scaling, we demonstrate substantial computational costs reductions (in comparison with the canonical EOM-CC3) in the case of two large molecules - l-proline and heptazine. This illustrates the usefulness of the RR-EOM-CC3 method for accurate determination of excitation energies of large molecules.

Analytic Gradients for Equation-of-Motion Coupled Cluster with Single, Double, and Perturbative Triple Excitations.

Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in determining the singlet-triplet gap of chromophores. However, a full understanding of excited-state processes requires additional explorations of the excited-state potential energy surface and electronic properties, which is greatly aided by the availability of analytic energy gradients. Owing to its robust high accuracy over a wide range of chemical problems, equation-of-motion coupled cluster with single and double excitations (EOM-CCSD) is a powerful method for predicting excited-state properties, and the implementation of analytic gradients of many EOM-CCSD variants (excitation energies, ionization potentials, electron attachment energies, etc.) along with numerous successful applications highlights the flexibility of the method. In specific cases where a higher level of accuracy is needed or in more complex electronic structures, the inclusion of triple excitations becomes essential, for example, in the EOM-CCSD* approach of Saeh and Stanton. In this work, we derive and implement for the first time the analytic gradients of EOMEE-CCSD*, which also provides a template for analytic gradients of related excited-state methods with perturbative triple excitations. The capabilities of analytic EOMEE-CCSD* gradients are illustrated by several representative examples.

Optimization of the thermoelectric performance of aluminum-doped zinc oxide-graphene heterojunctions under high temperature and high pressure

High-pressure effects can be used to effectively optimize the thermoelectric performance of wide-bandgap oxides. We build upon this finding to show that the synergistic effects of doping with aluminum and graphene composite give excellent thermoelectric performance under high pressure. By employing the parabolic band model, the Pisarenko curves are derived at different pressures, coupled with the band structure of Al-doped ZnO. An analysis indicates that pressure-induced narrowing of the bandgap in Al-doped ZnO reduces the electron excitation energy, thereby optimizing the electrical properties of the samples. The Debye Callaway model is also used to fit the lattice thermal conductivity of the samples, thus enabling an in-depth analysis of the phonon scattering mechanisms. Our analysis suggests that graphene composites significantly enhance point defect scattering and Umklapp scattering, thus increasing the phonon relaxation time and effectively reducing the lattice thermal conductivity of the samples. The improvement in the figure of merit (zT) of ZnO is attributed to the simultaneous enhancement of its electrical properties under high pressure and the synergistic optimization of reducing the lattice thermal conductivity through doping and composites. In this work, we consider a fixed doping ratio of Al and a constant proportion of graphene composite, and analyze the microstructure and thermoelectric properties of 0.1C–ZnAl0.04O (C–ZnAlO) samples synthesized under pressures ranging from 1 to 5 GPa, with the aim of elucidating the influence of pressure and graphene composite on the electro-acoustic transport properties of ZnO. We find that the zT value for a sample synthesized at 5 GPa is increased to 0.27 at 973 K.

The Pigment World: Life's Origins as Photon-Dissipating Pigments.

Many of the fundamental molecules of life share extraordinary pigment-like optical properties in the long-wavelength UV-C spectral region. These include strong photon absorption and rapid (sub-pico-second) dissipation of the induced electronic excitation energy into heat through peaked conical intersections. These properties have been attributed to a "natural selection" of molecules resistant to the dangerous UV-C light incident on Earth's surface during the Archean. In contrast, the "thermodynamic dissipation theory for the origin of life" argues that, far from being detrimental, UV-C light was, in fact, the thermodynamic potential driving the dissipative structuring of life at its origin. The optical properties were thus the thermodynamic "design goals" of microscopic dissipative structuring of organic UV-C pigments, today known as the "fundamental molecules of life", from common precursors under this light. This "UV-C Pigment World" evolved towards greater solar photon dissipation through more complex dissipative structuring pathways, eventually producing visible pigments to dissipate less energetic, but higher intensity, visible photons up to wavelengths of the "red edge". The propagation and dispersal of organic pigments, catalyzed by animals, and their coupling with abiotic dissipative processes, such as the water cycle, culminated in the apex photon dissipative structure, today's biosphere.

Theory for proton-coupled energy transfer.

In the recently discovered proton-coupled energy transfer (PCEnT) mechanism, the transfer of electronic excitation energy between donor and acceptor chromophores is coupled to a proton transfer reaction. Herein, we develop a general theory for PCEnT and derive an analytical expression for the nonadiabatic PCEnT rate constant. This theory treats the transferring hydrogen nucleus quantum mechanically and describes the PCEnT process in terms of nonadiabatic transitions between reactant and product electron-proton vibronic states. The rate constant is expressed as a summation over these vibronic states, and the contribution of each pair of vibronic states depends on the square of the vibronic coupling as well as the spectral convolution integral, which can be viewed as a generalization of the Förster-type spectral overlap integral for vibronic rather than electronic states. The convolution integral also accounts for the common vibrational modes shared by the donor and acceptor chromophores for intramolecular PCEnT. We apply this theory to model systems to investigate the key features of PCEnT processes. The excited vibronic states can contribute significantly to the total PCEnT rate constant, and the common modes can either slow down or speed up the process. Because the pairs of vibronic states that contribute the most to the PCEnT rate constant may correspond to spectroscopically dark states, PCEnT could occur even when there is no apparent overlap between the donor emission and acceptor absorption spectra. This theory will assist in the interpretation of experimental data and will guide the design of additional PCEnT systems.

Transfer of Electronic Excitation Energy Between Thioflavin T and Its Styryl Derivatives Incorporated Into Amyloid Fibrils

Transfer of Electronic Excitation Energy Between Thioflavin T and Its Styryl Derivatives Incorporated Into Amyloid Fibrils

Single-Electron Qubits Based on Quantum Ring States on Solid Neon Surface.

Single electrons trapped on solid-neon surfaces have recently emerged as a promising platform for charge qubits. Experimental results have revealed their exceptionally long coherence times, yet the actual quantum states of these trapped electrons, presumably on imperfectly flat neon surfaces, remain elusive. In this Letter, we examine the electron's interactions with neon surface topography, such as bumps and valleys. By evaluating the surface charges induced by the electron, we demonstrate its strong perpendicular binding to the neon surface. The Schrödinger equation for the electron's lateral motion on the curved 2D surface is then solved for extensive topographical variations. Our results reveal that surface bumps can naturally bind an electron, forming unique quantum ring states that align with experimental observations. We also show that the electron's excitation energy can be tuned using a modest magnetic field to facilitate qubit operation. This study offers a leap in our understanding of electron-on-solid-neon qubit properties and provides strategic insights on minimizing charge noise and scaling the system to propel forward quantum computing architectures.

Linear and nonlinear optical properties of hybrid Polyaniline/CoFe2O4 nanocomposites: Electrochemical synthesis, characterization, and analysis

This study presents a focused investigation and comprehensive analysis of the synthesis of hybrid Polyaniline/Cobalt ferrite (PANI/CoFe2O4) nanocomposites using an optimized electrochemical polymerization method. CoFe2O4 nanoparticles (NPs) were incorporated into the PANI matrix at varying concentrations (3, 6, and 12 wt%). The research examined the newly synthesized hybrid nanocomposites in terms of their structure, dielectric properties, and both linear and nonlinear optical properties. As a result of the Williamson-Hall method, the average crystallite size varied between 45 and 99 nm. Initially, adding a small quantity of NPs decreased the nanocomposite size, but further additions increased it due to aggregation. The Tauc plot showed a gradual increase in the energy band gap of the films as the concentration of CoFe2O4 NPs increased up to 12 wt%. This trend showed stronger absorption bands and higher coefficients, indicating improved light absorption compared to pure PANI films. Dielectric properties, including dielectric constants (ɛr, ɛi) and dielectric loss (tan δ), were examined as a function of frequency. The experimental results indicated that PANI/CoFe2O4 exhibited lower dielectric constants than bare PANI. Concentration-dependent optical properties, such as electronic transition excitation energies, dispersion energies, and optical conductivity, were also investigated. These properties were modeled using a single oscillator based on the Wemple-DiDomenico (WDD) approach. The study revealed a reduction in key optical parameters—linear susceptibility, nonlinear third-order susceptibility, and nonlinear refractive index—as nanoparticle content increased. Conversely, increasing concentrations of CoFe2O4 NPs led to a significant increase in the ratio of free carriers to effective mass (N/m٭), from 3.89 × 10³⁶ to 4.04 × 10³⁶ m⁻³ kg⁻1. Additionally, the electrical conductivity of both PANI and PANI/CoFe2O4 nanocomposites exhibited temperature-dependent improvement, reaching maximum values. The observed findings indicate that hybrid PANI-CoFe2O4 nanocomposites possess enhanced properties, highlighting their promising potential as active materials for a broad range of optoelectronic applications.

Performance of range-separated long-range SOPPA short-range density functional theory method for vertical excitation energies.

In this paper, benchmark results are presented on the calculation of vertical electronic excitation energies using a long-range second-order polarization propagator approximation (SOPPA) description with a short-range density functional theory description based on the Perdew-Burke-Ernzerhof (PBE) functional. The excitation energies are investigated for 132 singlet states and 71 triplet states across 28 medium-sized organic molecules. The results show that overall SOPPA-srPBE always performs better than PBE and that SOPPA-srPBE performs better than SOPPA for singlet states, but slightly worse than SOPPA for triplet states when CC3 results are the reference values.

Efficient removal of bisphenol A from water using a novel organic–inorganic hybrid heterojunction

Organic-inorganic hybrid heterojunctions have the ability to efficiently remove trace pollutants from water due to efficient photosensitivity. In this work, an organic–inorganic hybrid S-scheme heterojunction photosensitizer (RCP-BW) was successfully fabricated by growing cross-linked β-CD/riboflavin copolymer on the surface of bismuth tungstate (Bi2WO6). The fabrication of the copolymer retains the photosensitivity of riboflavin and the confinement effect of β-CD and forms an internal electric field with Bi2WO6 to enhance the photoelectron transport ability. Photogenerated electrons are transferred and stacked from Bi2WO6 to β-CD/riboflavin copolymers, which greatly enhances the ability of organic copolymers to reduce oxygen and produce superoxide radicals. We combined electrochemistry, free radical chemistry and DFT to study the photoelectron migration mechanism and photocatalytic performance enhancement mechanism in S-scheme heterojunctions. The pseudo-first-order reaction kinetic constant (kRCP-BW = 0.081 min−1) for BPA degradation was four times that of unmodified BW (kBW = 0.020 min−1). β-CD regulates the band structure of riboflavin to match with Bi2WO6, and utilizes charged contaminants and intermediate degradation products to promote the production of reactive oxygen species through interface electron transfer and excited state transition energy transfer. This work provides theoretical support and technical means for photocatalytic oxidation technology to control endocrine disruptors.

Glory interference spectroscopy in Sr atom

Slow (meV) photoelectron imaging spectroscopy is employed in the experimental study of near-threshold photoionization of strontium atoms in the presence of an external static electric field. Specifically, the study is devoted to the glory effect, that is, the appearance of an intense peak at the center of the recorded photoelectron images, when dealing with m= 0 final ionized Stark states (m denoting the magnetic quantum number). This critical effect is formally identical to that encountered in classical scattering theory, where, for a nonzero value of the impact parameter, the zero-crossing of the deflection function leads to a divergent classical differential cross section. By recording the magnitude variation of this glory peak as a function of electron excitation energy, we observe that, besides the traces of classical origin, it also exhibits intense quantum interference and beating phenomena, above and below the zero-static-field ionization threshold. We study both, single- and two-photon ionization of Sr, thus enabling a comparison not only between the different excitation schemes, but also with an earlier work devoted to two-photon ionization of Mg atom by Kalaitzis et al (2020 Phys. Rev. A 102 033101). Our recordings are analyzed within the framework of the Harmin–Fano frame transformation Stark effect theory that is applied to both the hydrogen atom and a non-hydrogenic one simulating Sr. We discuss the various aspects of the recorded and calculated glory interference and beating structures and their ‘short time Fourier transforms’ and classify them as either atom-specific or atom independent. In particular, we verify the ‘universal’ connection between the glory oscillations above the zero-field threshold and the differences between the origin-to-detector times of flight corresponding to pairs of classical electron trajectories that end up to the image center.

Antioxidative Triplet Excitation Energy Transfer in Bacterial Reaction Center Using a Screened Range Separated Hybrid Functional.

Excess energy absorbed by photosystems (PSs) can result in photoinduced oxidative damage. Transfer of such energy within the core pigments of the reaction center in the form of triplet excitation is important in regulating and preserving the functionality of PSs. In the bacterial reaction center (BRC), the special pair (P) is understood to act as the electron donor in a photoinduced charge transfer process, triggering the charge separation process through the photoactive branch A pigments that experience a higher polarizing environment. At this work, triplet excitation energy transfer (TEET) in BRC is studied using a computational perspective to gain insights into the roles of the dielectric environment and interpigment orientations. We find in agreement with experimental observations that TEET proceeds through branch B. The TEET process toward branch B pigment is found to be significantly faster than the hypothetical process proceeding through branch A pigments with ps and ms time scales, respectively. Our calculations find that conformational differences play a major role in this branch asymmetry in TEET, where the dielectric environment asymmetry plays only a secondary role in directing the TEET to proceed through branch B. We also address TEET processes asserting the role of carotenoid as the final triplet energy acceptor and in a mutant form, where the branch pigments adjacent to P are replaced by bacteriopheophytins. The necessary electronic excitation energies and electronic state couplings are calculated by the recently developed polarization-consistent framework combining a screened range-separated hybrid functional and a polarizable continuum mode. The polarization-consistent potential energy surfaces are used to parametrize the quantum mechanical approach, implementing Fermi's golden rule expression of the TEET rate calculations.

A variational reformulation of molecular properties in electronic-structure theory.

Conventional quantum-mechanical calculations of molecular properties, such as dipole moments and electronic excitation energies, give errors that depend linearly on the error in the wave function. An exception is the electronic energy, whose error depends quadratically on the error in wave function. We here describe how all properties may be calculated with a quadratic error, by setting up a variational Lagrangian for the property of interest. Because the construction of the Lagrangian is less expensive than the calculation of the wave function, this approach substantially improves the accuracy of quantum-chemical calculations without increasing cost. As illustrated for excitation energies, this approach enables the accurate calculation of molecular properties for larger systems, with a short time-to-solution and in a manner well suited for modern computer architectures.

Electronic structure, spectroscopy and photophysics of rubidium mono-sulphide

We investigated the nineteen first electronic states of the RbS diatomic using post Hartree-Fock configuration interaction methods at the internally contracted multi-reference configuration interaction (MRCI+(Q)) level. We thus mapped their respective potential energy curves with and without considering spin-orbit effects. After nuclear motion treatments, we derived their equilibrium distances, rotational and vibrational constants, and dissociation and electronic excitation energies. Moreover, an evaluation of the dipole moments of RbS was conducted, which in turn were used to evaluate the radiative lifetimes of the vibrational levels of RbS (X2П and A2Σ+) states. Computations show that spin-orbit interactions are important and cannot be omitted. Afterwards, and utilizing the sum rule approximation and the Franck–Condon factors, we computed both the bound-bound contributions and the bound-free terms. Our findings suggest that RbS exhibits intriguing characteristics suitable for laser cooling experiments. In sum, this work contributes to the understanding in-depth of the spectroscopy of RbS and predicts its use as a promising molecular system for laser cooling applications.

Structural and optical properties of ZnO thin films as a function of pH value and its effect on photoelectrochemical water splitting

ZnO nanoparticles were synthesised via sol–gel method, and then, deposited on a glass substrate using the spin-coating procedure to hand in ZnO thin films. In order to study the effect of alkaline sol on different properties of ZnO thin films, the pH value of sol was adjusted with ammonia. Then, the structural, optical, and photoelectrochemical properties of the prepared samples were analysed. According to XRD analyses, by increasing pH values, the size of ZnO particles increases and the films’ crystallinity improves. In addition, SEM micrographs affirm the uniformity of thin films. According to AFM findings, the morphology and roughness of the samples’ surface are affected by pH values in such a way that with increasing the pH, the roughness of the surface decreases, and the crystallinity improves. Also, both UV–vis peaks shift towards lower wavelengths with increasing pH value of ZnO sol. This means that the more the pH values of ZnO sol, the more the excitation energy of electrons. On the other hand, the numerical values of the energy bandgap decrease by increasing pH. According to PL results, the increase of pH causes the separated electrons and holes to have more energy and can move away from each other. So, the recombination process rate decreases; this result affirms by EIS findings. Increasing the optical absorption and reducing charge recombination are in favour of the photocatalytic reactions. Clearly, increasing the pH value causes the stable photocurrent to increase and the threshold voltage of (J-V) diagram to decrease. Also, the samples show recognisable sensitivity to light. As a final result, the best suggested amount of pH to fabricate ZnO photoanods for water splitting is 10.5.

How do spin-scaled double hybrids designed for excitation energies perform for noncovalent excited-state interactions? An investigation on aromatic excimer models.

Time-dependent double hybrids with spin-component or spin-opposite scaling to their second-order perturbative correlation correction have demonstrated competitive robustness in the computation of electronic excitation energies. Some of the most robust are those recently published by our group (M. Casanova-Páez, L. Goerigk, J. Chem. Theory Comput. 2021, 20, 5165). So far, the implementation of these functionals has not allowed correctly calculating their ground-state total energies. Herein, we define their correct spin-scaled ground-state energy expressions which enables us to test our methods on the noncovalent excited-state interaction energies of four aromatic excimers. A range of 22 double hybrids with and without spin scaling are compared to the reasonably accurate wavefunction reference from our previous work (A. C. Hancock, L. Goerigk, RSC Adv. 2023, 13, 35964). The impact of spin scaling is highly dependent on the underlying functional expression, however, the smallest overall errors belong to spin-scaled functionals with range separation: SCS- and SOS- PBEPP86, and SCS-RSX-QIDH. We additionally determine parameters for DFT-D3(BJ)/D4 ground-state dispersion corrections of these functionals, which reduce errors in most cases. We highlight the necessity of dispersion corrections for even the most robust TD-DFT methods but also point out that ground-state based corrections are insufficient to completely capture dispersion effects for excited-state interaction energies.

The solvatochromic effect of functionalized 6-aminoracil derivatives in light of DFT: FT-IR, TD-DFT, NBO, and FMO studies

Uracil-based compounds have increasing attention in material design for different applications as well as pharmaceutical purposes. Accordingly, the key electronic reasons underlying the solvatochromic effect and possible activity features by using quantum chemical computations should be explored in detail. This work focuses on the structural, electronic, and optical properties of the aminouracil derivatives to explore the key electronic-related properties that affect the solvatochromism features. The molecular geometries of the 1,3-dimethyl-5-(arylazo)-6-aminouracil derivatives were optimized using the DFT method at the B3LYP/6–31++G(d,p) basis set level. The solvent-phase simulations of the studied derivatives were utilized using the PCM (Polarized Continuum Model). The TD-DFT approach was employed to enlighten UV–visible characteristics such as possible electronic transitions, energies, and oscillator strengths. The NBO (Natural Bond Orbital) method was used to predict the possible intramolecular charge transfer and delocalization, as well as the interactions between donor-acceptor molecular orbitals. TD-DFT computations revealed that the bonded group within the arylazo ring would affect solvatochromic properties such as electronic excitation energies and transitions in the UV-Vis regions. The NBO analysis revealed that the electron movement from the lone pair of N atoms on the uracil unit to neighbor unfilled orbitals contributed to reducing the stabilization energy.

Spectral and conformational characteristics of phycocyanin associated with changes of medium pH.

C-phycocyanin (C-PC) is the main component of water-soluble light-harvesting complexes (phycobilisomes, PBS) of cyanobacteria. PBS are involved in the absorption of quantum energy and the transfer of electronic excitation energy to the photosystems. A specific environment of C-PC chromophoric groups is provided by the protein matrix structure including protein-protein contacts between different subunits. Registration of C-PC spectral characteristics and the fluorescence anisotropy decay have revealed a significant pH influence on the chromophore microenvironment: at pH 5.0, a chromophore is more significantly interacts with the solvent, whereas at pH 9.0 the chromophore microenvironment becomes more viscous. Conformations of chromophores and the C-PC protein matrix have been studied by Raman and infrared spectroscopy. A decrease in the medium pH results in changes in the secondary structure either the C-PC apoproteins and chromophores, the last one adopts a more folded conformation.