Oscillator Strength Distribution Research Articles

Electrical control of excitonic oscillator strength and spatial distribution in a monolayer semiconductor

Electrical control of excitonic oscillator strength and spatial distribution in a monolayer semiconductor

Evaluation of the mean excitation energies of gaseous and liquid argon

Current and future experiments need to know the stopping power of liquid argon. It is used directly in calibration, where commonly the minimum-ionizing portion of muon tracks is used as a standard candle. Similarly, muon range is used as a measure of muon energy. More broadly, the stopping power figures into the simulation of all charged particles, and so uncertainty propagates widely throughout data analysis of all sorts. The main parameter that controls stopping power is the mean excitation energy, or I-value. Direct experimental information for argon's I-value come primarily from measurements of gaseous argon, with a very limited amount of information from solid argon, and none from liquid argon. A powerful source of indirect information is also available from oscillator strength distribution calculations. We perform a new calculation and find that from oscillator strength information alone, the I-value of gaseous argon is (187 ± 5) eV. In combination with the direct measurements and other calculations, we recommend (187 ± 4) eV for gaseous argon. For liquid argon, we evaluate the difference in central value and uncertainty incurred by the difference of phase and recommend (197 ± 7) eV. All uncertainties are given to 68% C.L.

Dipole–Dipole Polarizability of the Cadmium 1S0 State Revisited

Experimental results and high-level quantum chemical ab initio calculations of the static polarizability $\alpha_0=\alpha(\omega=0)$ of the cadmium ${^1S_0}$ state are still in marked disagreement. Here we analyze this discrepancy by using experimentally determined dipole oscillator strength distributions (DOSD). It will be shown that within this procedure the experimentally determined static polarizability $\alpha_0$ will shift from $49.7 \pm 1.6~$au to considerably lower values. We now conclude an experimentally determined polarizability of $\alpha_0=47.5 \pm 2.0~$au in much better agreement with the latest calculations of $\alpha_0 \approx 46~$au.

Ultrastrong Exciton-Photon Coupling in Broadband Solar Absorbers.

The recent development of organic polaritonic solar cells, in which sunlight absorbers and photon modes of a resonator are hybridized as a result of their strong coupling, has revealed the potential this interaction offers to control and enhance the performance of these devices. In this approach, the photovoltaic cell is built in such a way that it also behaves as an optical cavity supporting spectrally well-defined resonances, which match the broad absorption bands of the dyes employed. Herein we focus on the experimental and theoretical analysis of the specific spectral and angular optical absorption characteristics of a broadband light harvester, namely a subphthalocyanine, when operating in the ultrastrong coupling regime. We discuss the implications of having a broad distribution of oscillator strengths and demonstrate that rational design of the layered structure is needed to optimize both the spectral and the angular response of the sunlight harvester dye.

Dipole-dipole polarizability of the cadmium -=SUP=-1-=/SUP=-S-=SUB=-0-=/SUB=- state revisited -=SUP=-*-=/SUP=-

Experimental results and high-level quantum chemical ab initio calculations of the static polarizability α=α(ω=0)) of the cadmium 1S0 state are still in marked disagreement. Here we analyze this discrepancy by using experimentally determined dipole oscillator strength distributions (DOSD). It will be shown that within this procedure the experimentally determined static polarizability α0 will shift from 49.7± 1.6 au to considerably lower values. We now conclude an experimentally determined polarizability of α0 = 47.5 ± 2.0 au in much better agreement with the latest calculations of α0~ 46 au. Keywords: cadmium, polarizability, DOSD

Dipole oscillator strength distributions, sum rules, mean excitation energies, and isotropic van der Waals coefficients for benzene, pyridazine, pyrimidine, pyrazine, s-triazine, toluene, hexafluorobenzene, and nitrobenzene

Experimental, theoretical, and additive-model photoabsorption cross sections combined with constraints provided by the Kuhn-Reiche-Thomas sum rule and the high-energy behavior of the dipole oscillator strength density are used to construct dipole oscillator strength distributions for benzene, pyridazine (1,2-diazine), pyrimidine (1,3-diazine), pyrazine (1,4-diazine), s-triazine (1,3,5-triazine), toluene (methylbenzene), hexafluorobenzene, and nitrobenzene. The distributions are used to predict dipole sum rules S(k) for -6 ≤ k ≤ 2, mean excitation energies I(k) for -2 ≤ k ≤ 2, and isotropic van der Waals C6 coefficients. A popular combination rule for estimating C6 coefficients for unlike interactions from the C6 coefficients of the like interactions is found to be accurate to better than 1% for 606 of 628 cases (96.4%) in the test set.

Optical Absorption Cross-Section of DNA Bases—Thymine and Guanine—in the Energy Region from 3.1 to 250 eV (5–400 nm)

(1) Background: Optical absorption cross-section—the absolute absorption intensity specific to each molecule—of nucleic acid bases enables us to estimate the reaction yields of DNA lesions induced by the exposure to not only photons but also ionizing radiations. However, it was unknown in the energy region exceeding ~10 eV (wavelength < ~120 nm). (2) Methods: Thin films of DNA bases—thymine and guanine—were prepared using a vacuum sublimation technique. Absorption spectra of these films were measured in the energy region from 3.1 to 250 eV (5–400 nm) at the synchrotron radiation facility UVSOR. (3) Results: The absorption spectra of both bases exhibited prominent absorption peaks around 20 eV and smaller peaks in the energy region below 10 eV. The determined optical oscillator strength distribution was verified to be reasonable based on the Thomas–Reiche–Kuhn oscillator strength sum rule. (4) Conclusion: Most of the oscillator strength distribution was positioned in the measured energy region, and therefore the absorption spectra significantly contributed to the quantitative study for the photo and radiation-chemical reactions of DNA.

Distribution of oscillator strengths and correlated electron dynamics in artificial atoms

The electronic structure of the quasi-two-dimensional disk-like artificial atom involving holes inside has been studied by the full configuration interaction (FCI) wave function employing mixed basis sets consisting of standard atomic orbitals and anisotropic Gaussian-type functions. The one-particle confinement potential for electrons has been modeled by a sum of an anisotropic harmonic-oscillator potential and attractive Coulomb potentials, the latter being responsible for the hole positive charges. The oscillator strengths from the ground state to a number of low-lying excited states have been calculated by the FCI energies and wave functions for different strength of the harmonic confinement ω. The results for two electrons with a hole at the center, namely, the He-like system, have shown accumulation of the oscillator strengths distributed among different dipole-allowed transitions in the excitation into the center-of-mass modes or the plasmon modes for increasing confinement strength ω. The system of two electrons with two impurity holes, namely, the H2-like system, has been also studied, which has shown a far more complicated trend of the oscillator strengths with respect to ω owing to the additional degree of freedom of the internuclear distance r. The observed trend has been rationalized on the basis of the nodal patterns in the molecular orbitals and in the electron density distributions.

Distribution of dipole oscillator strengths for the formation of excited hydrogen atom from C2H2

SynopsisDipole oscillator strengths for the formation of excited hydrogen atom from C2H2 were measured to investigate formation and decay of molecular superexcited states. It seems that non-adiabatic transition plays an important role in the formations of the hot hydrogen atom.

Spectral Distribution of Oscillator Strength for Core-to-Valence Transitions probed by using X-ray Absorption and Total Electron Yield Modes

Abstract Changes in spectral distribution of oscillator strength for core-to-valence transitions probed by X-ray absorption and total electron yield (TEY) modes are studied in more detail. The quantitative analysis of their redistribution in TEY due to the saturation effect is performed by applying the model M ˜ $\tilde M$ -function method suggested by Flesch et al. J. Chem. Phys. 138 (2013) 144302. The model M ˜ $\tilde M$ -function method is generalized to account for the saturation-induced distortion of the line shape of the transitions embedded into the core ionization continua and located below them. It is shown that TEY measurements produce essential changes not only in the relative intensity of the transitions but also shift upward the transition energy, broaden the Lorentzian and Gaussian widths and enhance the line asymmetry. The Gaussian width of the TEY signal undergoes the most substantial broadening though the Lorentzian width increases significantly too. The saturation-induced distortion of the line shapes is not negligible even if the well-known escape-to-penetration condition is valid.

Thermal changes in young and mature bone nanostructure probed with Ca 2p excitations

Thermal dependence of mineralized bone structure is examined both experimentally by measuring the near edge x-ray absorption fine structure (NEXAFS) and theoretically by applying the 3DSL model to clarify relationship between the local electronic and atomic structure and hierarchical organization of skeleton. The high energy resolution NEXAFS spectra are acquired near the Ca 2p edges in native bone heated from RT up to 450 °C and hydroxyapatite (Ca10(PO4)6(OH)2, OH-Ap) to understand the interplay of short-, long- and super-range order parameters of bone matter. Our focus is on the thermal changes of spectral distribution of oscillator strength for Ca 2p1/2,3/2 → 3d transition in bone and OH-Ap. The investigations have confirmed the assignment of the OH-Ap-to-bone spectral changes to the predicted hierarchy effect on electronic and atomic structure of mineralized bone. At RT the OH-Ap-to-bone red shift of the transition energy is found equal ≈ 0.2 eV and ≈ 0.1 eV for mature and young bone respectively. We stated that the shift behaves irregular and its magnitude varies from 0.1 eV up to 0.3 eV when the heating temperature grows. Two mechanisms associated with the thermal-induced dehydration of the inter-nanocrystallite spaces and with the subsequent atomic restructuring of the nanocrystallite interface in mineralized phase are revealed. We have detected that the OH-Ap-to-bone red shifts of the Ca 2p → 3d transition in young bone are smaller than those of in mature bone. The origin of the age differences is discussed.

Derived properties from the dipole and generalized oscillator strength distributions of an endohedral confined hydrogen atom

We report the electronic properties of a hydrogen atom confined by a fullerene molecule by obtaining the eigenvalues and eigenfunctions of the time-independent Schrödinger equation by means of a finite-differences approach. The hydrogen atom confinement by a C60 fullerene cavity is accounted for by two model potentials: a square-well and a Woods–Saxon. The Woods–Saxon potential is implemented to study the role of a smooth cavity on the hydrogen atom generalized oscillator strength distribution. Both models characterize the cavity by an inner radius R0, thickness Δ, and well depth V0. We use two different values for R0 and Δ, found in the literature, that characterize H@C60 to analyze the role of the fullerene cage size and width. The electronic properties of the confined hydrogen atom are reported as a function of the well depth V0, emulating different electronic configurations of the endohedral cavity. We report results for the hyper-fine splitting, nuclear magnetic screening, dipole oscillator strength, the static and dynamic polarizability, mean excitation energy, photo-ionization, and stopping cross section for the confined hydrogen atom. We find that there is a critical potential well depth value around V0 = 0.7 a.u. for the first set of parameters and around V0 = 0.9 a.u. for the second set of parameters, which produce a drastic change in the electronic properties of the endohedral hydrogen system. These values correspond to the first avoided crossing on the energy levels. Furthermore, a clear discrepancy is found between the square-well and Woods–Saxon model potential results on the hydrogen atom generalized oscillator strength due to the square-well discontinuity. These differences are reflected in the stopping cross section for protons colliding with H@C60.

Medium-induced change of the optical response of metal clusters in rare-gas matrices

Interaction with the surrounding medium modifies the optical response of embedded metal clusters. For clusters from about ten to a few hundreds of silver atoms, embedded in rare-gas matrices, we study the environment effect within the matrix random phase approximation with exact exchange (RPAE) quantum approach, which has proved successful for free silver clusters. The polarizable surrounding medium screens the residual two-body RPAE interaction, adds a polarization term to the one-body potential, and shifts the vacuum energy of the active delocalized valence electrons. Within this model, we calculate the dipole oscillator strength distribution for Ag clusters embedded in helium droplets, neon, argon, krypton, and xenon matrices. The main contribution to the dipole surface plasmon red shift originates from the rare-gas polarization screening of the two-body interaction. The large size limit of the dipole surface plasmon agrees well with the classical prediction.

Rayleigh scattering in dense fluid helium

Iglesias et al. (2002) showed that the Rayleigh scattering from helium atoms decreases by collective effects in the atmospheres of cool white dwarf stars. Their study is here extended to consider an accurate evaluation of the atomic polarizability and the density effects involved in the Rayleigh cross section over a wide density-temperature region. The dynamic dipole polarizability of helium atoms in the ground state is determinated with the oscillator-strength distribution approach. The spectral density of oscillator strength considered includes most significant single and doubly excited transitions to discrete and continuum energies. Static and dynamic polarizability results are confronted with experiments and other theoretical evaluations shown a very good agreement. In addition, the refractive index of helium is evaluated with the Lorentz-Lorenz equation and shows a satisfactory agreement with the most recent experiments. The effect of spatial correlation of atoms on the Rayleigh scattering is calculated with Monte Carlo simulations and effective energy potentials that represent the particle interactions, covering fluid densities between 0.005 and a few g/cm$^3$ and temperatures between $1000$ K and $15000$ K. We provide analytical fits from which the Rayleigh cross section of fluid helium can be easily calculated at wavelength $\lambda>505.35$ \AA. Collision-induced light scattering was estimated to be the dominant scattering process at densities greater than 1-2 g/cm$^3$ depending on the temperature.

Ab initio calculations of exciton effects in optical spectra of an α-B12 crystal

The dielectric functions and energy loss spectrum of electrons of a rhombohedral α-B12 crystal are studied both in the single-particle and many-particle approximations using Bethe–Salpeter equations. The opposite roles of different contributions to exciton effects are discussed. The anisotropy of dielectric functions is shown, which demonstrates their high sensitivity with respect to the three-dimensional packing of icosahedrons. The influence of the coherent mixing of electronic and exciton states on the redistribution of oscillator strengths is found. The position of the plasmon of valence electrons and the high-frequency permittivity are found to be consistent with experimental data. The correlation between the distribution of oscillator strengths and features of the density of electronic states is discussed.

Static polarizabilities and C6 dispersion coefficients using the algebraic-diagrammatic construction scheme for the complex polarization propagator

An implementation of the damped linear response function, or complex polarization propagator, using the algebraic-diagrammatic construction (ADC) scheme has been developed and utilized for the calculation of electric-dipole polarizabilities and C6 dispersion coefficients. Four noble gases (He, Ne, Ar, and Kr), five n-alkanes (methane, ethane, propane, butane, and pentane), three carbonyls (formaldehyde, acetaldehyde, and acetone), and three unsaturated hydrocarbons (ethene, acetylene, and benzene) have been treated with the hierarchical set of models ADC(2), ADC(2)-x, and ADC(3/2), and comparison has been made to results obtained with damped linear response Hartree–Fock (HF) and coupled cluster singles and doubles (CCSD) theory as well as high-quality experimental estimates via the dipole oscillator strength distribution approach. This study marks the first ADC calculations of C6 dispersion coefficients and the first ADC(3/2) calculations of static polarizabilities. Results at CCSD and ADC(3/2) levels of theory are shown to be of similar quality, with electron correlation effects increasing the molecular property values for all calculations except CCSD considerations of ethene and acetylene (attributed to an overestimation of bond electron density at HF level of theory). The discrepancies between CCSD and ADC(3/2) are partially due to ADC overestimating anisotropies, and discrepancies with respect to experimental values are partially due to the lack of zero-point vibrational effects in the present study.

Lindhard's polarization parameter and atomic sum rules in the local plasma approximation: a case for excited states

ABSTRACTIn this work, we analyze the effects of Lindhard polarization parameter, χ, on the sum rule, , within the local plasma approximation (LPA) as well as on the logarithmic sum rule , in both cases for the system in an initial excited state. We show results for a hydrogenic atom with nuclear charge Z for the spherically symmetric (l=0) states with n=1, 2 and 3 with p=−1,0,1, and 2. Our calculations are complemented with comparisons to the exact results for this system for the ground state. As a natural extension of our treatment, we report analytical results for helium-like systems in terms of a screened charge for the ground state. Our study shows that by increasing χ, the sum rule for p<0 decreases while for p>0 it increases, and the value p=0 provides the normalization/closure relation which remains fixed to the number of electrons for the same initial state. When p is fixed, the value of increases as the initial excited state increases for p<0 and decreases for p>0. Thus, when using a specific value of χ to adjust to a particular sum rule value, the sum rule becomes unbalanced for other values of p. Our results show that the dipole oscillator strength distribution, within the LPA, provides good results for the sum rules for excited states.

Constrained dipole oscillator strength distributions, sum rules, and dispersion coefficients for Br2 and BrCN

Dipole oscillator strength distributions for Br2 and BrCN are constructed from photoabsorption cross-sections combined with constraints provided by the Kuhn-Reiche-Thomas sum rule, the high-energy behavior of the dipole-oscillator-strength density and molar refractivity data when available. The distributions are used to predict dipole sum rules S(k), mean excitation energies I(k), and van der Waals C6 coefficients. Coupled-cluster calculations of the static dipole polarizabilities of Br2 and BrCN are reported for comparison with the values of S(-2) extracted from the distributions.

Constrained Dipole Oscillator Strength Distributions for CF4, CClF3, CCl2F2, CCl3F, CHF3, CH3F, CH3Cl, CH3Br, CH3I, C2F6, and CCl3CF3

Abstract Dipole oscillator strength distributions are constructed for CF4, CClF3, CCl2F2, CCl3F, CHF3, CH3F, CH3Cl, CH3Br, CH3I, C2F6, and CCl3CF3 from experimental and theoretical photoabsorption cross-sections combined with constraints provided by the Kuhn–Reiche–Thomas sum rule, the high-energy behavior of the dipole-oscillator-strength density, and either molar refractivity data or static dipole polarizabilities depending upon the availability of refractivities. The distributions are used to predict dipole sum rules S(k), mean excitation energies I(k), and van der Waals C 6 coefficients. Pseudospectral representations of the DOSDs are reported.

Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra.

The effectiveness of solar energy capture and conversion materials derives from their ability to absorb light and to transform the excitation energy into energy stored in free carriers or chemical bonds. The Thomas-Reiche-Kuhn (TRK) sum rule mandates that the integrated (electronic) oscillator strength of an absorber equals the total number of electrons in the structure. Typical molecular chromophores place only about 1% of their oscillator strength in the UV-vis window, so individual chromophores operate at about 1% of their theoretical limit. We explore the distribution of oscillator strength as a function of excitation energy to understand this circumstance. To this aim, we use familiar independent-electron model Hamiltonians as well as first-principles electronic structure methods. While model Hamiltonians capture the qualitative electronic spectra associated with π electron chromophores, these Hamiltonians mistakenly focus the oscillator strength in the fewest low-energy transitions. Advanced electronic structure methods, in contrast, spread the oscillator strength over a very wide excitation energy range, including transitions to Rydberg and continuum states, consistent with experiment. Our analysis rationalizes the low oscillator strength in the UV-vis spectral region in molecules, a step toward the goal of oscillator strength manipulation and focusing.