Valence Electron Excitation Research Articles

Wide spectral range optical characterization of niobium pentoxide ([formula omitted]) films by universal dispersion model

In this work, the optical properties of niobium pentoxide (Nb2O5) films were extensively studied across a wide spectral range using heterogeneous data-processing methods, combining ellipsometric and spectrophotometric measurements for five samples with thicknesses between 20 and 250 nm. This study primarily determined the optical constants of Nb2O5 from the far infrared to the vacuum ultraviolet, presenting these constants as dispersion parameters using the universal dispersion model to describe valence electron excitations in ultraviolet region as well as phonon vibrations in infrared region. These comprehensive and reliable data across such a broad spectral range are unprecedented. Secondly, presented optical characterization proofs that Nb2O5 films can be grown without defects such as surface roughness, porosity, or inhomogeneity. This fact, together with its high refractive index, makes Nb2O5 a promising material for optical applications.

UV-VUV absorption spectra of azido-based energetic plasticizer bis(1,3-diazido prop-2-yl)malonate in gas phase.

Ultraviolet and vacuum ultraviolet photo-absorption spectra of azido (-N3)-based energetic plasticizer, bis(1,3-diazido-prop-2-yl)-malonate (abbreviated as BDAzPM), in the gas phase is recorded at room temperature and in the photon energy range of 5.5-9.9eV using a synchrotron radiation source. Complementary computational results obtained using the time-dependent density functional theory document the vertical transition energies and oscillator strengths. Comparison of the simulated spectra with the experimental absorption spectrum of BDAzPM reveals that the early part of the absorption spectrum of BDAzPM is of pure valence excitation character, whereas the later intense part of the absorption spectrum is dominated by mixed Rydberg and valence electronic excitations.

Electromagnetically Induced Transparency Spectra of 6Li Rydberg Atoms

Rydberg atoms possess highly excited valence electrons that are far away from atomic cations. Compared with ground states, Rydberg states are excited states with a high principal quantum number n that exhibit large electric dipole moments and have a variety of applications in quantum information processing. In this communication, we report the measurement of the 6Li Rydberg excitation spectrum by ladder-type electromagnetically induced transparency (EIT) in a vapor cell. The 2p→ns/nd EIT spectra were recorded by sweeping the frequency of an ultraviolet Rydberg pumping laser while keeping the probing laser resonant to the 2s→2p transition. All lasers were locked on an ultrastable optical Fabry-Pérot cavity and measured by an optical frequency comb. Our results provide valuable information to precisely determine quantum defects and enable novel experiments with Rydberg-dressed ultracold Fermi gases.

Aromatic-Free Polymers Based All-Organic Dielectrics with Breakdown Self-Healing for High-Temperature Capacitive Energy Storage.

High-temperature dielectric polymers are becoming increasingly desirable for capacitive energy storage in renewable energy utilization, electrified transportation, and pulse power systems. Current dielectric polymers typically require robust aromatic molecular frameworks to ensure structural thermal stability at elevated temperatures. Nevertheless, the introduction of aromatic units compromises electrical insulation owing to pronounced π─π interactions that facilitate electron transport and eliminate the breakdown self-healing property owing to their high carbon content. Herein, an aromatic-free polynorborne copolymer exhibiting electrical conductivity-two orders of magnitude lower than that of state-of-the-art polyetherimide-at elevated temperatures and high electric fields owing to its large bandgap (≈4.64eV) and short hopping conduction distance (≈0.63nm) is described. Density functional theory calculations demonstrate that the copolymer can effectively suppress the excitation of high-field valence electrons. Furthermore, the incorporation of trace semiconductors results in high discharge density (3.73Jcm-3 ) and charge-discharge efficiency (95% at 150°C), outperforming existing high-temperature dielectric polymers. The excellent electrical breakdown self-healing capability of the copolymer film at elevated temperatures further demonstrates its potential for use in dielectric capacitors capable of continuous operation under extreme conditions.

Band engineering in monoclinic WO3 with C+H co-doping for optoelectronic applications: A hybrid functional study

Using the hybrid functional method, we systematically investigate the band engineering induced by C + H co-doping in monoclinic WO3, and the associated effect on the optoelectronic functionality as well. First, we find that C substitution for O in WO3 improves the optical absorption through narrowing the band gap by 11% and introducing a curved intermediate level within the band gap (which functions as a stepping stone to relay the excited valence electrons to the conduction band). Further H incorporation into C-doped WO3 stabilizes the C substitution via clustering with C in the form of C-H and H-C-H chains, which reduces the band gap to less than 2 eV and simultaneously drives the deep C-induced intermediate level to be shallow. Such dopant clustering and the induced band engineering remarkably promote the optical absorption and optoelectronic functionality of WO3. The positive influence of dopant clustering has been fully analysed and discussed, and the favorability for forming C-H and H-C-H clusters in WO3 has been well presented through the detailed thermodynamic and kinetic analyses. The outcome of this work is expected to offer insightful guidance to tuning the properties of WO3 materials towards optoelectronic applications.

Pseudopotential Bethe-Salpeter calculations for shallow-core x-ray absorption near-edge structures: Excitonic effects in α−Al2O3

We present an ab initio description of optical and shallow-core x-ray absorption spectroscopies in a unified formalism based on the pseudopotential plane-wave method at the level of the Bethe-Salpeter equation (BSE) within Green's functions theory. We show that norm-conserving pseudopotentials are reliable and accurate not only for valence, but also for semicore electron excitations. In order to validate our approach, we compare BSE absorption spectra obtained with two different codes: the pseudopotential-based code EXC and the all-electron full-potential code Exciting. We take corundum $\alpha$-Al$_2$O$_3$ as an example, being a prototypical material that presents strong electron-hole interactions for both valence and core electron excitations. We analyze in detail the optical absorption spectrum as well as the Al L$_1$ and L$_{2,3}$ edges in terms of anisotropy, crystal local fields, interference and excitonic effects. We perform a thorough inspection of the origin and localization of the lowest-energy excitons, and conclude highlighting the purely electronic character off the pre-edge of L$_1$ and the dichroic nature of the optical and L$_{23}$ spectra.

5p1/2nℓj autoionizing states of strontium for 0≤ℓ≤5

We report a comprehensive experimental and theoretical study of the autoionization of core-excited $5{p}_{1/2}n{\ensuremath{\ell}}_{j}$ strontium Rydberg states for intermediate values of ${\ensuremath{\ell}}_{j}$ in the range $0\ensuremath{\lesssim}{\ensuremath{\ell}}_{j}\ensuremath{\lesssim}5$. For a given value of ${\ensuremath{\ell}}_{j}$ autoionization, which results from the energy exchange between the two excited valence electrons, is found to scale as $\ensuremath{\sim}1/{n}^{3}$, mirroring the decrease in the Rydberg electron probability density in the vicinity of the inner $5{p}_{1/2}$ electron cloud. In contrast, the ${\ensuremath{\ell}}_{j}$ dependence of the autoionization rate is more complex. For the larger values of ${\ensuremath{\ell}}_{j}$ $(\ensuremath{\ge}4)$, the autoionization rate decreases as ${\ensuremath{\ell}}_{j}^{\ensuremath{-}5}$ due to the centrifugal barrier, which prevents the Rydberg electron from penetrating the core and inner $5{p}_{1/2}$ electron cloud. For the low-${\ensuremath{\ell}}_{j}$ core-penetrating Rydberg states, the scattering phase shift induced by the effective core potential becomes important in determining both the autoionization rates, which no longer show a monotonic variation with ${\ensuremath{\ell}}_{j}$, and the quantum defects.

Measuring autoionization decay lifetimes of optically forbidden inner valence excited states in neon atoms with attosecond noncollinear four-wave-mixing spectroscopy

Attosecond noncollinear four wave mixing spectroscopy with one attosecond extreme ultraviolet (XUV) pulse and two few-cycle near-infrared (NIR) pulses was used to measure the autoionization decay lifetimes of inner valence electronic excitations in neon atoms. After a 43-48 eV XUV photon excites a 2s electron into the 2s2p6[np] Rydberg series, broadband NIR pulses couple the 2s2p6[3p] XUV-bright state to neighboring 2s2p6[3s] and 2s2p6[3d] XUV-dark states. Controllable delays of one or both NIR pulses with respect to the attosecond XUV pulse reveal the temporal evolution of either the dark or bright states, respectively. Experimental lifetimes for the 3s, 3p, and 3d states are measured to be 7 +/- 2 fs, 48 +/- 8 fs, and 427 +/- 40 fs, respectively, with 95% confidence. Accompanying calculations with two independent ab initio theoretical methods, NewStock and ASTRA, verify the findings. The results support the expected trend that the autoionization lifetime should be longer for states that have a smaller penetration in the radial region of the 2s core hole, which in this case is for the higher angular momentum Rydberg orbitals. The underlying theory thus links the lifetime results to electron correlation and provides an assessment of the direct and exchange terms in the autoionization process.

Effects of semicore electrons on stopping power in helium-irradiated aluminum nanosheets.

The stopping power of energetic He ions traversing an Al film is studied by combining the time-dependent density-functional theory method with molecular dynamics simulations. We investigated the dependence of the semicore electron excitation of the Al film on the projectile's trajectory and its charge state. Our results show that for the off-channeling trajectories the semicore electrons contribute significantly to the stopping power of the Al film as the He+ ion velocity exceeds 1.0 a.u, and in contrast, it is negligible for the channeling trajectories. Most importantly, we found two unexpected effects of semicore electrons on the stopping power in helium-irradiated aluminum nanosheets, i.e., (1) the semicore electrons can contribute to the energy loss for both high and low energy projectiles under the off-channeling trajectory; (2) as the projectile velocity increases from 0.4 a.u. to 2.0 a.u. although semicore electron excitation (including transition in the target, ionization away from the target and transfer to the projectile ion) of the target atom is gradually inhibited, the influence of semicore electrons on valence electron excitation is gradually enhanced. Our finding allows us to gain new insights into the stopping of ions in metals.

Laser-induced valence electron excitation in acetylene

Strong-field induced valence electron excitation is a common process in strong field interaction with atoms and molecules. In the case of polyatomic molecules, the effects of ionization from low-lying molecular orbitals and nuclear dynamics during the interaction can play critical roles for electron excitation. In this work, we investigate the involved molecular orbitals in the electron excitation of singly ionized acetylene in a strong laser field using alignment dependence and laser intensity dependence. Additionally, the involved nuclear dynamics during the electron excitation are identified from the difference in the kinetic energy release and the angular distribution of laser-induced dissociation with different pulse durations and intensities. The laser intensity dependence clearly shows the relative strength change of two excitation pathways in the measured momentum and angle-resolved distributions.

Photoexcitation-Induced Nonthermal Ultrafast Loss of Long-Range Order in GeTe.

Nonadiabatic quantum molecular dynamics is used to investigate the evolution of GeTe photoexcited states. Results reveal a photoexcitation-induced picosecond nonthermal path for the loss of long-range order. A valence electron excitation threshold of 4% is found to trigger local disorder by switching Ge atoms from octahedral to tetrahedral sites and promoting Ge-Ge bonding. The resulting loss of long-range order for a higher valence electron excitation fraction is achieved without fulfilling the Lindemann criterion for melting, therefore utilizing a nonthermal path. The photoexcitation-induced structural disorder is accompanied by charge transfer from Te to Ge, Ge-Te bonding-to-antibonding, and Ge-Ge antibonding-to-bonding change, triggering Ge-Te bond breaking and promoting the formation of Ge-Ge wrong bonds. These results provide an electronic-structure basis to understand the photoexcitation-induced ultrafast changes in the structure and properties of GeTe and other phase-change materials.

First-principles study of the electronic stopping power of indium for protons and He ions

The electronic stopping power of protons and He ions traveling along the channeling and off-channeling trajectories in indium is reported based on time-dependent density functional theory combined with Ehrenfest molecular dynamics simulations. We provided an intuitive description of the electronic stopping power for a wide range of ion energies, and revealed the microcosmic excitation mechanism of the semicore $4d$ electrons of In. The velocity-proportional electronic stopping power and the kink velocity which is due to $4d$-electron excitation are reproduced in the low-energy regime. Because the $5s5p$ valence electrons are uniformly distributed in indium, the electronic excitation of valence electrons via Coulomb scattering is independent of the impact parameter in the investigated velocity range. On the contrary, due to the highly localized nature of semicore electrons, the excitation of $4d$ electrons increases significantly with decreasing of the impact parameter, which suggests that it is triggered by direct ion-electron collision. Our calculated stopping power is in quantitative agreement with the experimental data up to the stopping maximum, and showed that the stopping power obtained from the off-channeling geometry is greatly improved in comparison with the channeling results. Finally, we examined the extent to which the linear response theory is applicable to describe the electronic stopping power by quantifying the velocity dependence of the mean steady-state charge of protons and $\ensuremath{\alpha}$ particles and the effective charge state for $\ensuremath{\alpha}$ particles, and it is found that the linear response theory can be used to predict the stopping power in a wider energy range if the mean steady-state charge is used instead of assuming fully ionized charges.

Chromium‐Based Metal–Organic Framework as A‐Site Cation in CsPbI2Br Perovskite Solar Cells

AbstractInorganic CsPbIxBr3−x perovskite solar cells (PSCs) have gained enormous interest due to their excellent thermal stabilities. However, their intrinsically poor moisture stability hampers their further development. Herein, a chromium‐based metal–organic framework group is intercalated inside the inorganic PbI framework, resulting in a new multiple‐dimensional electronically coupled CsPbI2Br perovskite. In this structurally and electronically coupled perovskite, the π‐conjugated terpyridyl can delocalize the excited valence electrons of metal Cr3+ ion, enabling multi‐interactive charge‐carrier transport channels within CsPbI2Br perovskites. The stability and efficiency of the produced devices are substantially enhanced in comparison to their counterparts with only a pristine CsPbI2Br active layer. The optimized all‐inorganic PSC yields a power conversion efficiency (PCE) as high as 17.02%. Remarkably, the stabilized device retains 80% of its PCE after 1000 h in the ambient atmosphere. This study provides a new paradigm toward addressing the stability challenge of the inorganic perovskite while enhancing its carrier transport ability.

The Critical Number of Gold Atoms for a Metallic State Nanocluster: Resolving a Decades-Long Question.

Probing the transition from a metallic state to a molecular state in gold nanoparticles is fundamentally important for understanding the origin of surface plasmon resonance and the nature of the metallic bond. Atomically precise gold nanoclusters are desired for probing such a transition based upon a series of precise sizes with X-ray structures. While the definition of the metallic state in nanoclusters is simple, that is, when the HOMO-LUMO gap (Eg) becomes negligibly small (Eg < kBT, where kB is the Boltzmann constant and T the temperature), the experimental determination of ultrasmall Eg (e.g., of kBT level) is difficult, and the thermal excitation of valence electrons apparently comes into play in ultrasmall Eg nanoclusters. Although a sharp transition from nonmetallic Au246(SR)80 to metallic Au279(SR)84 (SR: thiolate) has been observed, there is still uncertainty about the transition region. Here, we summarize several criteria on determining the metallic state versus the molecular (or nonmetallic) state in gold nanoclusters, including (1) Eg determined by optical and electrochemical methods, (2) steady-state absorption spectra, (3) cryogenic optical spectra, (4) transient absorption spectra, (5) excited-state lifetime and power dependence, and (6) coherent oscillations in ultrafast electron dynamics. We emphasize that multiple analyses should be performed and cross-checked in practice because no single criterion is definitive. We also review the photophysics of several gold nanoclusters with nascent surface plasmon resonance. These criteria are expected to deepen the understanding of the metallic to molecular state transition of gold and other metal nanoclusters and also promote the design of functional nanomaterials and their applications.

Electronic structure of reduced CeO2(111) surfaces interacting with hydrogen as revealed through electron energy loss spectroscopy in comparison with theoretical investigations

Based on both, ab-initio cluster calculations as well as periodic density functional based loss function calculations, we have assigned the origins of the valence electron excitation regime in electron energy loss spectra of well-ordered ceria films in (111) orientation at various states of reduction as well as after exposing the reduced films to hydrogen from the gas phase (Li et al, Angew. Chem. Int. Ed., 58 (2019) 14686–14693). The explicit calculation of intensity distributions using the dipole approximation allow us to draw conclusions about the nature of oxygen vacancies, which occur upon reduction and how those interact with hydrogen to form hydride species.The present study also reports a brief discussion of vibrational excitations of hydrogen loaded ceria and corroborates previous interpretations, based on inelastic neutron scattering.

Insights into the sputter-instigated valence plasmon oscillations in CIGSe thin films

We report a unique methodology of triggering plasmonic excitations in sputtered ultrathin CIGSe films. In this approach of plasmonic excitation, secondary ion source present in the growth system instigates the formation of nanoclusters of its constituent elements, which is the source of plasmonic excitation. The formation of the nanoclusters during the growth is because of the distinct sputtering out rates of the various elements during the growth. For the verification of valence electron excitation and plasmonic oscillations, the studies performed as follows: a) investigation of electron energy loss from the ultraviolet-photoelectron spectroscopy measurements, b) quantification of the various electron energy loss contributions associated with the constituent element present in the films within the observed broad peaks in ultravoilet photoelectron spectroscopy (UPS) spectrum, c) estimation of particular plasmon contribution, i.e., particle, valence-surface, and valence-bulk plasmon at the air/thin-film interface, and within the thin film, d) verification of plasmonic behavior by analyzing different optical properties performing spectroscopic ellipsometry measurements, 5) validation of the nanocluster emergence in ultrathin CIGSe thin films deploying Field Emission Scanning Electron Microscopy. This approach is promising in terms of improving the solar cell performance parameters by supplementing the optical path length within the absorber in the broad spectral range without the need of externally supplied metal nanoparticles.

Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities.

We demonstrate how optical cavities can be exploited to control both valence- and core-excitations in a prototypical model transition metal complex, ferricyanide ([Fe(iii)(CN)6]3−), in an aqueous environment. The spectroscopic signatures of hybrid light-matter polariton states are revealed in UV/Vis and X-ray absorption, and stimulated X-ray Raman signals. In an UV/Vis cavity, the absorption spectrum exhibits the single-polariton states arising from the cavity photon mode coupling to both resonant and off-resonant valence-excited states. We further show that nonlinear stimulated X-ray Raman signals can selectively probe the bipolariton states via cavity-modified Fe core-excited states. This unveils the correlation between valence polaritons and dressed core-excitations. In an X-ray cavity, core-polaritons are generated and their correlations with the bare valence-excitations appear in the linear and nonlinear X-ray spectra.

Fourier-Transform VUV Spectroscopy of 14,15N and 12,13C

Accurate Fourier-transform spectroscopic absorption measurements of vacuum ultraviolet transitions in atomic nitrogen and carbon were performed at the Soleil synchrotron. For 14N, transitions from the 2s22p34S3/2 ground state and from the 2s22p32P and 2D metastable states were determined in the 95–124 nm range at an accuracy of 0.025cm−1. The combination of these results with data from previous precision laser experiments in the vacuum ultraviolet range reveals an overall and consistent offset of −0.04 cm−1 from values reported in the NIST database. The splittings of the 2s22p34S3/2 – 2s2p44PJ transitions are well-resolved for 14N and 15N and the isotope shifts determined. While excitation of a 2p valence electron yields very small isotope shifts, excitation of a 2s core electron results in large isotope shifts, in agreement with theoretical predictions. For carbon, six transitions from the ground 2s22p23PJ and 2s22p3s3PJ excited states at 165 nm are measured for both 12C and 13C isotopes.

Guanine-adenine interactions in DNA tetranucleotide cation radicals revealed by UV/vis photodissociation action spectroscopy and theory.

Hydrogen-rich cation radicals (GATT + 2H)+˙ and (AGTT + 2H)+˙ represent oligonucleotide models of charged hydrogen atom adducts to DNA. These tetranucleotide cation radicals were generated in the gas phase by one-electron reduction of the respective (GATT + 2H)2+ and (AGTT + 2H)2+ dications in which the charging protons were placed on the guanine and adenine nucleobases. We used wavelength-dependent UV/Vis photodissociation in the valence-electron excitation region of 210-700 nm to produce action spectra of (GATT + 2H)+˙ and (AGTT + 2H)+˙ that showed radical-associated absorption bands in the near-UV (330 nm) and visible (400-440 nm) regions. Born-Oppenheimer molecular dynamics and density-functional theory calculations were used to obtain and rank by energy multiple (GATT + 2H) dication and cation-radical structures. Time-dependent density functional theory (TD-DFT) calculations of excited-state energies and electronic transitions in (GATT + 2H)+˙ were augmented by vibronic spectra calculations at 310 K for selected low-energy cation radicals to provide a match with the action spectrum. The stable product of one-electron reduction was identified as having a 7,8-dihydroguanine cation radical moiety, formed by intramolecular hydrogen atom migration from adenine N-1-H. The hydrogen migration was calculated to have a transition state with a low activation energy, Ea = 96.5 kJ mol-1, and positive activation entropy, ΔS‡ = 75 J mol-1 K-1. This allowed for a fast isomerization of the primary reduction products on the ion-trap time scale of 150 ms that was substantially accelerated by highly exothermic electron transfer.

Optical absorption and excitation spectra of monolayer blue phosphorene

We study the optical absorption and excitation spectra of monolayer blue phosphorene with two approaches. The first is based on the approximation in conjunction with the Bethe–Salpeter equation theory. The second is based on the time-dependent density-functional theory in the adiabatic local density approximation and the random phase approximation. The spectra from the two approaches are quite similar. The optical absorption spectrum is dominated by a single peak at 4.2 eV, which originates from direct interband transitions at the point of the Brillouin zone. The excitation spectrum is dominated by a plasmon peak at 9.2 eV, which arises from collective excitations of valence electrons. The plasmon shows a positive dispersion at finite momentum transfer. The in-plane electron is responsible for the optical absorption, whereas the out-of-plane electron is responsible for the plasmon dispersion. Monolayer blue phosphorene has an indirect band gap of 2.98 eV and an exciton binding energy of 1.03 eV.