Excited-state Density Research Articles

Electronic Descriptors for Supervised Spectroscopic Predictions.

Spectroscopic properties of molecules hold great importance for the description of the molecular response under the effect of UV/vis electromagnetic radiation. Computationally expensive ab initio (e.g., MultiConfigurational SCF, Coupled Cluster) or TDDFT methods are commonly used by the quantum chemistry community to compute these properties. In this work, we propose a (supervised) Machine Learning approach to model the absorption spectra of organic molecules. Several supervised ML methods have been tested such as Kernel Ridge Regression (KRR), Multiperceptron Neural Networs (MLP), and Convolutional Neural Networks. [Ramakrishnan et al. J. Chem. Phys. 2015, 143, 084111. Ghosh et al. Adv. Sci. 2019, 6, 1801367.] The use of only geometrical-atomic number descriptors (e.g., Coulomb Matrix) proved to be insufficient for an accurate training. [Ramakrishnan et al. J. Chem. Phys. 2015, 143, 084111.] Inspired by the TDDFT theory, we propose to use a set of electronic descriptors obtained from low-cost DFT methods: orbital energy differences (Δϵia = ϵa - ϵi), transition dipole moment between occupied and unoccupied Kohn-Sham orbitals (⟨ϕi|r|ϕa⟩), and when relevant, charge-transfer character of monoexcitations (Ria). We demonstrate that with these electronic descriptors and the use of Neural Networks we can predict not only a density of excited states but also get a very good estimation of the absorption spectrum and charge-transfer character of the electronic excited states, reaching results close to chemical accuracy (∼2 kcal/mol or ∼0.1 eV).

Rules of thumb for synthesizing superheavy elements

Synthesizing any elements in the eighth period using either cold or hot fusion reactions remains a big challenge to date. The quasifission mechanism restricts complete fusion to an indeterminably low evaporation residue (ER) cross-section for superheavy nuclei. The entrance channel parameters of the heavy-ion reaction, the fission barrier of the compound nucleus, the deformation parameters of the projectile and target nuclei, and the kinetic energy of the projectile are mainly responsible for governing the scale of the quasifission. The role of these factors has been examined explicitly by the experimental ER cross-sections. Thorough comparisons lead us to infer that the entrance channel criteria contribute to a much lower extent than the deformation parameters do. The effect of deformation can be categorized into four rules as validated by all the reactions used except one Uue. The null result from this reaction is explained by the improper choice of the projectile energy, as shown theoretically by means of a statistical model approach, which is valid for a system having a large nucleon number so as to intrinsically have a high density of excited states. The optimal selection of the beam energy sets another rule. Therefore, these five rules can be treated as the rules of thumb for synthesizing the superheavy elements. Application of the first four rules can enable us primarily to spot a suitable reaction, and finally, exploitation of the fifth rule chooses the most appropriate reaction at a preferable excited energy to achieve the highest ER cross-section for a superheavy element.

Enhancement of intrinsic optical transitions in silicon nanocrystals by state localization

Silicon photoluminescence and lasing have been critical issues to breakthrough bottlenecks in the understanding of luminescence mechanisms. Unfortunately, long-standing disputes about the exciton recombination mechanism and fluorescence lifetime remain unresolved, especially about whether silicon nanocrystals (Si NCs) can realize fast direct-bandgap-like optical transitions. Here, using ground-state and excited-state density functional theory (DFT), we obtained intrinsic phonon-free optical transitions at sizes from Si22 to Si705, showing that very small Si NCs can realize a strong direct optical transition. Orbital labeling results show that this rapid transition does not come from the {\Gamma}-{\Gamma} -like transition, contrary to the conclusions from the effective mass approximation (EMA) and that {\Gamma}-X mixing leads to a quasi-direct bandgap. This anomalous transition is particularly intense with decreasing size (or enhancement of quantum confinement). By investigating electron and hole distributions generated in the optical transition, localized state-induced enhanced emission (LIEE) in Si NCs was proposed. Quantum confinement (QC) distorts the excited-state electron spatial distribution by localizing Bloch waves into the NC core, resulting in increased hole and electron overlap, thus inducing a fast optical process. This work resolves important debates and proposes LIEE to explain the anomalous luminescence--a phase transition from weak (or none) luminescent state to strong optical transition, which will aid attempts at realizing high-radiative-rate NCs materials and application-level Si lasers.

Evaluation of a collisional radiative model for electron temperature determination in hydrogen plasma.

A collisional-radiative (CR) model that extracts the electron temperature, Te, of hydrogen plasmas from Balmer-line-ratio measurements is examined for the plasma electron density, ne, and Te ranges of 1010-1015 cm-3 and 5-500eV, respectively. The CR code, developed and implemented in Python, has a forward component that computes the densities of excited states up to n = 15 as functions of Te, ne, and the molecular-to-atomic neutral ratio r(H2/H). The backward component provides ne and r(H2/H) as functions of the Balmer ratios to predict the Te. The model assumes Maxwellian electrons. The density profiles of the electrons and of the molecular and atomic hydrogen neutrals are shown to be of great importance, as is the accuracy of the line-ratio measurement method.

Anti-Kasha Fluorescence in Molecular Entities: Central Role of Electron-Vibrational Coupling.

According to Kasha's rule, the emission of a photon in a molecular system always comes from the lowest excited state. A corollary of this rule (i.e., the Kasha-Vavilov rule) states that the emission spectra are independent of the excitation wavelength. Although these rules apply for most of the molecular systems, violations of these rules are often reported. The prototypical case of a Kasha's rule violation is the fluorescence observed from S2 in azulene. Thanks to the advances in both theoretical and experimental research, other types of anomalous fluorescence (e.g., excitation energy transfer (EET)-based dual emissions, thermally activated fluorescence, etc.) are more recurrently reported in the literature. Sometimes, these anomalous processes involve higher-lying excited states but are mechanistically different from the azulene-like anomalous fluorescence. However, the underlying mechanisms leading to these anomalous emissions can be numerous and are not yet well understood.In order to shed some light on the above phenomena, this Account provides a comprehensive review of this topic. We herein report quantum chemical investigations in target molecular systems breaking Kasha's rule. The latter molecules were chosen because they were unambiguously reported to display anti-Kasha fluorescence. Our studies highlight three different types of anti-Kasha scenarios. Specifically, (i) the strong electronic, weak vibrational nonadiabatic coupling (NAC) regime (here named the type I case, i.e., azulene-like); (ii) the strong electronic, strong vibrational NAC regime (type II case, i.e., thermally activated S2 fluorescence); and the (iii) very weak electronic NAC regime (type III case, i.e., EET dyads). In addition, by combining state-of-the-art quantum chemical calculations with excited-state decay rate theories and appropriate excited-state kinetic models, we provide semiquantitative estimations of photoluminescence quantum yields for the most rigid molecular entities. Finally, we propose the use of simple theoretical descriptors relying on calculations of the excited-state density difference and the electron-vibrational coupling to classify anomalous emissions according to their coupling scenario.Besides the fundamental interest of the above investigations, the herein developed computational protocols and descriptors will be useful for the tailored design of dyes with tunable and unconventional fluorescence properties and their exploitation in a wide range of areas (i.e., from organic light-emitting diodes (OLEDs) to bioimaging, small-molecule fluorescent probes, and photocatalysis). Finally, our theoretical framework enables the attainment of a holistic understanding of the interconversion processes between excited states, where the electron-vibrational coupling is shown to play a central role in determining the efficacy.

Three new turn-on fluorescent sensors for the selective detection of Zn2+: Synthesis, properties and DFT studies

The design and synthesis of three new 1,8-naphthalimide-based fluorescent sensors ( 1 – 3 ) for the detection of Zn 2+ in aqueous solution is described. The structural architect of these sensors contains 1,8-naphthalimide scaffold as a fluorophore attached to 2,2′-dipicolylamine (DPA) and bis(2-quinolinylmethyl)amine (DQA) receptors through an amide linkage. The addition of Zn 2+ to the solutions of sensors ( 1 – 3 ) led to enhanced fluorescence intensity, ranging between 2.5 and 14 folds. At physiological pH (pH = 7.4), these sensors exhibited high selectivities for Zn 2+ over a wide range of competing metal cations, displaying high sensitivities with a limit of detections of 120, 81.7 and 79.2 nM, respectively. This suggests that these sensors can detect chronic Zn 2+ concentration for freshwater ( > 1.84 μM), designated by the U.S. Environmental Protection Agency. DFT simulations performed on the more stable stacked conformations of unbound and Zn 2+ bounded states suggested that the latter display higher density of excited states than the unbound sensors. Moreover, the stacked conformer of sensor 3 was significantly more stable as compared to sensors 1 and 2 , which was attributed to a stronger Van Der Waals (VDW) interaction between DQA and 1,8-naphthalimide. The Zn 2+ binding leads to enhanced electronic coupling between the HOMOs and LUMOs, making excited states more populated which then undergoes geometric relaxation before emitting light and relaxing back to the ground states. The lower energy separation (5.0 eV) between the HOMO and the first Zn 2+ d-orbital in sensor 3 as compared to sensors 1 and 2 results in enhanced density of the generated states and subsequently higher intensity upon binding with Zn 2+ .

Optical diagnosis of a kHz-driven helium atmospheric pressure plasma jet

This paper focuses on utilizing several different optical diagnostics to experimentally characterize a pure helium atmospheric pressure plasma jet. Axial electric field measurements were carried out along the plasma plume through the use of a non-perturbing method based on polarization-dependent Stark spectroscopy of the helium $492.2$ nm line. The electric field is shown to increase with distance along the plume length, reaching values as high as $24.5$ kV cm $^{-1}$ . The rate of increase of the electric field is dependent on the helium gas flow rate, with lower gas flows rising quicker with distance in comparison with larger flow rates, with the typical values remaining within the same range. This sensitivity is linked to gas mixing between the helium and surrounding ambient air. Schlieren imaging of the gas flow is included to support this. The addition of a target is shown to further increase the measured electric field in close range to the target, with the magnitude of this increase being strongly dependent on the distance between the tube exit and target. The relative increase in the electric field is shown to be on average greater for a conducting target of water in comparison with plastic. A minimal equipment optical configuration, which is here referred to as fast two-dimensional monochromatic imaging, is introduced as an approach for estimating excited state densities within the plasma. Densities of the upper helium states for transitions, $1s3s$ $^{3}S_{1}$ $\rightarrow$ $1s2p$ $^{3}P^{0}_{0,1,2}$ at $706.5$ nm and $1s3s$ $^{1}S_{0}$ $\rightarrow$ $1s2p$ $^{1}P^{0}_{1}$ at $728.1$ nm, were estimated using this approach and found to be of the order of $10^{10}$ – $10^{11}$ cm $^{-3}$ .

Spin-vibronic coupling in the quantum dynamics of a Fe(III) trigonal-bipyramidal complex.

The presence of a high density of excited electronic states in the immediate vicinity of the optically bright state of a molecule paves the way for numerous photo-relaxation channels. In transition-metal complexes, the presence of heavy atoms results in a stronger spin-orbit coupling, which enables spin forbidden spin-crossover processes to compete with the spin-allowed internal conversion processes. However, no matter how effectively the states cross around the Franck-Condon region, the degree of vibronic coupling, of both relativistic and non-relativistic nature, drives the population distribution among these states. One such case is demonstrated in this work for the intermediate-spin Fe(III) trigonal-bipyramidal complex. A quantum dynamical investigation of the photo-deactivation mechanism in the Fe(III) system is presented using the multi-configurational time-dependent Hartree approach based on the vibronic Hamiltonian whose coupling terms are derived from the state-averaged complete active space self-consistent field/complete active space with second-order perturbation theory (CASPT2) calculations and spin-orbit coupling of the scalar-relativistic CASPT2 states. The results of this study show that the presence of a strong (non-relativistic) vibronic coupling between the optically bright intermediate-spin state and other low-lying states of the same spin-multiplicity overpowers the spin-orbit coupling between the intermediate-spin and high-spin states, thereby lowering the chances of spin-crossover while exhibiting ultrafast relaxation among the intermediate-spin states. In a special case, where the population transfer pathway via the non-relativistic vibronic coupling is blocked, the probability of the spin-crossover is found to increase. This suggests that a careful modification of the complex by incorporation of heavier atoms with stronger relativistic effects can enhance the spin-crossover potential of Fe(III) intermediate-spin complexes.

On the population density of the argon excited levels in a high power impulse magnetron sputtering discharge

Population densities of excited states of argon atoms in a high power impulse magnetron sputtering (HiPIMS) discharge are examined using a global discharge model and a collisional-radiative model. Here, the ionization region model (IRM) and the Orsay Boltzmann equation for electrons coupled with ionization and excited states kinetics (OBELIX) model are combined to obtain the population densities of the excited levels of the argon atom in a HiPIMS discharge. The IRM is a global plasma chemistry model based on particle and energy conservation of HiPIMS discharges. OBELIX is a collisional-radiative model where the electron energy distribution is calculated self-consistently from an isotropic Boltzmann equation. The collisional model constitutes 65 individual and effective excited levels of the argon atom. We demonstrate that the reduced population density of high-lying excited argon states scales with (p*)−6, where p* is the effective quantum number, indicating the presence of a multistep ladder-like excitation scheme, also called an excitation saturation. The reason for this is the dominance of electron impact processes in the population and de-population of high-lying argon states in combination with a negligible electron–ion recombination.

Surface discharge of bulk materials investigated from change of charge trap characteristics of polyimide single molecular chain

Surface discharge is one of the reasons for insulation failure. Polyimide (PI) is used in gas-solid insulation of high-frequency electric power equipment. Therefore, based on density functional theory, the effects of single molecular chain structure, energy level, density of states, electrostatic potential, excited state and other micro parameters under external electric field on trap formation and surface discharge of both PI and polar- group- OH<sup>– </sup>affected PI are discussed from the atomic and molecular level. The results show that the structure of PI is crimped and the dipole moment increases under external electric field, which is easy to accumulate charges to form space charge center, especially after the introduction of polar group OH<sup>–</sup>. In the PI molecules, hole traps are formed in the benzene ring region, and electron traps are formed in the imide ring region. The number of electron trap energy levels is large, in which the space charge trap depth gradually deepens with the increase of external electric field. After the introduction of polar group OH<sup>–</sup>, the excitation energy of PI molecules decreases, which makes the electrons inside the molecules excited easily. The spatial separation of electrons and holes decreases with the increase of electric field, which is conducive to the recombination of holes and electrons to emit photons.

Nanoarchitectonics of Metal-Free Porous Polyketone as Photocatalytic Assemblies for Artificial Photosynthesis.

The main component of natural gas is methane, whose combustion contributes to global warming. As such, sustainable, energy-efficient, nonfossil-based methane production is needed to satisfy current energy demands and chemical feedstocks. In this article, we have constructed a metal-free porous polyketone (TPA-DPA PPK) with donor-acceptor (D-A) groups with an extensive π-conjugation by facile Friedel-Crafts acylation reaction between triphenylamine (TPA) and pyridine-2,6-dicarbonyl dichloride (DPA). TPA-DPA PPK is a metal-free catalyst for visible-light-driven CO2 photoreduction to CH4, which can be used as a solar fuel in the absence of any cocatalyst and sacrificial agent. CH4 production (152.65 ppm g-1) is ∼5 times greater than that of g-C3N4 under the same test conditions. Charge-density difference plots from excited-state time-dependent density functional theory (TD-DFT) calculations indicate a depletion and accumulation of charge density among the donor/acceptor functional groups upon photoexcitation. Most notably, binding energies from DFT demonstrate that H2O is more strongly bound with the pyridinic nitrogen group than CO2, which shed insight into mechanistic pathways for photocatalytic CO2 reduction.

Designing Direct Z-Scheme Heterojunctions Enabled by Edge-Modified Phosphorene Nanoribbons for Photocatalytic Overall Water Splitting.

Direct Z-scheme photocatalyst possess promising potential to utilize solar radiation for photocatalytic overall water splitting; however, the design and characterization remain challenging. Here, we construct and verify a direct Z-scheme heterojunction using edge-modified phosphorene-nanoribbons (X-PNRs, where X = OH and OCN) with first-principles ground-state and excited-state density functional theory (DFT) calculations. The ground-state calculations provide fundamental properties such as geometric structure and band alignment. The linear-response time-dependent DFT (LR-TDDFT) calculations exhibit the photogenerated charge distribution and demonstrate the generation of interlayer excitons in heterojunctions, which are advantageous to the electron-hole recombination in Z-scheme heterojunctions. The ultrafast charge transfer at the interface studied by time-dependent ab initio nonadiabatic molecular dynamics (NAMD) simulations indicates that interlayer electron-hole recombination is prior to intralayer recombination for the OH/OCN-PNRs heterojunction, showing the characteristics of a Z-scheme heterojunction. Therefore, our computational work provides a universal strategy to design direct Z-scheme heterojunction photocatalysts for overall water splitting.

Emerging Designs of Aggregation-Induced Emission Agents for Enhanced Phototherapy Applications

Emerging Designs of Aggregation-Induced Emission Agents for Enhanced Phototherapy Applications

Confinement on the optical response in h-BNCs: Towards highly efficient SERS-active 2D substrates

Several experimental and theoretical studies have shown that 2D hybrid structures formed by boron, nitrogen and carbon atoms (h-BNCs) possess a highly tunable linear and non-linear optical responses. Recent advances towards the controlled synthesis of these unique structures have motivated an important number of experimental and theoretical work. In this work, the confinement on the optical response induced by boron-nitride (BN) strings in h-BNC 2D structures is investigated using time-dependent density functional theory (TDDFT) and electron density response properties. The number of surrounding BN strings (NBN) necessary to “isolate” the optical modes of a carbon nanoisland (nanographene) from the remaining substrate has been characterized in two different nanoisland models: benzene and pyrene. It was found that for NBN ≥ 3 the excitation wavelengths of the optically active modes remain constant and the changes in the transition densities, the ground to excited state density differences and their associated electron deformation orbitals are negligible and strongly confined within the carbon nanoisland. Using a water molecule as model system, Raman enhancement factors of 10 [6] for the water vibrational modes are obtained when these electromagnetic “hot spots” are activated by an external electromagnetic field. The high tunability of the optical absorption bands of nanographenes through changes in size and morphology makes h-BNCs be perfect materials to construct platforms for surface enhancement Raman spectroscopy (SERS) for a wide range of laser sources.

Iodide vs Chloride: The Impact of Different Lead Halides on the Solution Chemistry of Perovskite Precursors

Controlled perovskite growth from solution is crucial for efficient optoelectronic applications and requires a deep understanding of the perovskite precursor chemistry. The so-called “chlorine route” to lead–iodide perovskite, using PbCl2 or MACl additive as a precursor, is frequently employed to form homogeneous perovskite layers by retarding perovskite crystallization. To understand the role of chlorine-containing lead precursors in solution, we analyze the chemical interaction of PbCl2 and PbI2 precursors with commonly employed solvents (γ-butyrolactone (GBL), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO)) by combining first-principles simulations and experimental UV–vis spectroscopy in diluted precursor solutions. Ab initio molecular dynamics simulations reveal reduced solvation and an increased free energy barrier of lead-halide bond dissociation of PbCl2 compared to PbI2 with chlorine acting as a stronger ligand, which, in turn, limits the solvent coordination. In contrast to PbI2, PbCl2 absorption spectra lack signatures of high-valent [PbCln]2–n complexes and show low sensitivity on the employed solvent, as confirmed by combined UV–vis and excited-state time-dependent density functional theory (TD-DFT) analysis. Altogether, our data suggest the presence of residual chlorine coordinated to Pb even in the presence of high iodine excess, which may retard the perovskite growth and could also lead to chlorine incorporation within the lead–iodide perovskite crystal.

Diagnostics of a high-pressure DC magnetron argon discharge with an aluminium cathode

In this article, the plasma parameters of a direct current magnetron discharge in argon at moderate pressure (10 to 40 Pa) using an aluminium cathode are explored. The density of argon excited states, the sputtered aluminium atom density and the electron temperature are estimated using a collisional–radiative model. The electron temperature obtained using optical emission spectroscopic data agrees well with measurements taken using a Langmuir probe. The influence of the discharge parameters, namely the background argon pressure and the discharge current, are discussed.

Spectroscopic and Quantum Chemical Investigations of Hypothetical m-Diacetylaminoazopyrimidine and Its Photovoltaic Properties

Abstract: Here, an attempt is made to theoretically study and predict the electronic and spectroscopic (UV-Vis and IR) and structural properties, quantum chemical descriptors and subsequent application of diacetylaminoazopyrimidine in dye-sensitized solar cells (DSSCs). Ground- and excited-state time-dependent density functional theory (TD-DFT) calculations were carried out using material studio and ORCA software, respectively. The computed ground-state energy gap, chemical hardness, chemical softness, chemical potential, electronegativity and electrophilicity index are: 3.60 eV, 1.80 eV, 0.56 eV, 4.49 eV, -4.49 eV and 5.68, respectively. Conversely, the DFT-predicted excited-state quantum chemical descriptors are: 1.67 eV, 0.83 eV, 1.20 eV, 4.71 eV and -4.71 eV, corresponding to the energy gap, chemical hardness, chemical softness, chemical potential and electronegativity, respectively. Furthermore, vibrational frequency calculations confirm the presence of some key functional groups (N=N, C=O, C-H) present in the dye molecules. The computed optoelectronic parameters, such as light-harvesting efficiency, electron injection and open-circuit voltage are 0.06 eV, -8.59 eV and -5.75 eV, respectively. Overall, the dye possesses a relatively good current conversion efficiency as compared to other dyes studied in the literature; hence, it could be used as a novel material for photovoltaic technological applications. Keywords: Diacetylaminoazopyrimidine, DFT, Excited state, Spectroscopy, DSSCs.

Ultrafast x-ray pump x-ray probe transient absorption spectroscopy: A computational study and proposed experiment probing core-valence electronic correlations in solvated complexes.

Femtosecond x-ray pump-x-ray probe experiments are currently possible at free electron lasers such as the linac coherent light source, which opens new opportunities for studying solvated transition metal complexes. In order to make the most effective use of these kinds of experiments, it is necessary to determine which chemical properties an x-ray probe pulse will measure. We have combined electron cascade calculations and excited-state time-dependent density functional theory calculations to predict the initial state prepared by an x-ray pump and the subsequent x-ray probe spectra at the Fe K-edge in the solvated model transition metal complex, K4FeII(CN)6. We find several key spectral features that report on the ligand-field splitting and the 3p and 3d electron interactions. We then show how these features could be measured in an experiment.

An improved collision - radiation model of the OH spectrum in the ultraviolet band

In order to calculate the spectral radiation characteristics of OH(A2∑) molecules more accurately, an improved collision-radiation (C-R) model is proposed to determine the excited states OH(A) number density. The six-components air model (CO, CO2, H2, H2O, N2, and O2) instead of the two-components air model (N2 and O2) are used as other plume products in the excitation/de-excitation radiation reaction, and the rate of the four reactions are modified to improve the accuracy and applicability of the number density. Effects of temperature and other plume products on the number density of excited states are analyzed in the experiment, and the spectral radiation characteristics of OH(A) can be obtained by using this improved C-R model. Results of these calculations are then compared with other series of experimental data of exhaust plume and shock layer, the results show that both the original model and the improved model can be used to calculate the radiation characteristics in shock layer, however, due to the great error, the original model not apply to calculation of the OH(A) number density in exhaust plume, and the result of the improved model is in good agreement with the Atlas experimental data. As the vibrational-rotational level distribution number density has a close relationship with radiative spectral characteristics, a more focused OH(A) particle number density model will be more helpful to the hypersonic target detection and recognition.

Neutral atom density measurements of xenon plasma inside a μ10 microwave ion thruster using two-photon laser-induced fluorescence spectroscopy

This paper reports measurements of the xenon ground state and excited state densities inside a μ10 microwave ion thruster. This thruster exhibits a 40% thrust enhancement upon changing from the waveguide to the discharge chamber propellant injection mode. In the present work, the associated mechanism was quantitatively evaluated using two-photon laser induced fluorescence (TALIF) spectroscopy to monitor the thruster waveguide. The 834.7 nm emission from excited state xenon was investigated with a 224.3 nm dye laser to excite the Xe I 5p61 S0 6pʹ [3/2]2 state, compared with the emission without the laser. The resulting data confirm that the neutral density exhibits a linear relationship with the propellant flow rate in the cold gas and ionized state, while the ion acceleration decreases the neutral density by the same order of magnitude as the propellant utilization efficiency is changed. As the propellant flow rate increases, the collisions of neutrals that generate excited states occur in the waveguide and, when this process plateaus, the ground state emission suddenly increases. Propellant injection from the discharge chamber is evidently effective at suppressing collisions with electrons in the waveguide that generate excited states and that potentially interfere with microwave propagation.