eV Excitation Energy Research Articles

Ellagic acid/Fe nanocomposite thin film with high power conversion efficiency for photovoltaic devices

This study synthesizes and characterizes an ellagic acid/Fe nanocomposite thin film ([Ellag-A/Fe·6H2O]NCTF) to enhance photovoltaic device efficiency, achieving a notable power conversion efficiency of 14.5 %. Using FT-IR, TGA, XRD, SEM, and optical analyses, the nanocomposite's structural, thermal, and optical properties were investigated, revealing a polycrystalline structure with improved thermal stability over pure ellagic acid. Density Functional Theory (DFT) calculations show a large energy gap of 1.08 eV, indicating stability and high excitation energies. The combination of organic ellagic acid with iron nanoparticles makes ([Ellag-A/Fe·6H2O]NCTF a promising material for photovoltaic applications.

UV Absorption Spectroscopy of the Conformer-Dependent Reactivity of the Four Carbon Criegee Intermediate of Methyl Vinyl Ketone Oxide: An Ab initio Quantum Dynamics Study.

An extended theoretical analysis of the photodissociation dynamics of the four-carbon Criegee intermediate (CH2═CH(CH3)COO) or methyl vinyl ketone oxide, which has four conformers, following excitation to the B state, is presented. Our analysis relies on multireference electronic wave functions combined with a wavepacket propagation treatment for the two coupled B1A' and C1A' electronic states and two nuclear degrees of freedom. For each conformer, the 2D model depends on potential energy surfaces (PESs) along the O-O and C-O-O bending modes for the two lowest excited states, B1A' and C1A', and is sufficiently accurate to reproduce the experimental B1A' ← X1A' absorption spectrum with unprecedented accuracy. It is found that the roles of each conformer are essential in producing a cumulative spectrum, which is close to the recent experimental spectrum. The anti-trans and anti-cis conformers make contributions at the longer and shorter wavelengths of the cumulative spectrum, respectively, while the syn-cis and syn-trans conformers have contributions in the middle wavelength range of the cumulative spectrum of MVK-oxide. The existence of a deep well for each conformer on the PESs of the (diabatic) B state causes a considerable amount of the wavepacket to be reflected by the B state wells, which can explain the oscillatory structures appearing in the long wavelength range of 360-480 nm of the spectrum. The weakly avoided crossings between the B-state and C-state PESs of each conformer appearing within the range of 2.80-3.08 eV excitation energy cause considerable disturbance in the vibronic fine structure of the bands. The results give novel insight into the complex interactions governing this intriguing process.

Raman spectroscopy of a few layers of bismuth telluride nanoplatelets.

We can shape the electronic and phonon properties of Bi2Te3 crystals via the variation of the number of layers. Here, we report a Raman study with the aid of first-principles calculations on few-layered Bi2Te3 systems ranging from 5 to 24 nm layer thickness using 1.92, 2.41 and 2.54 eV excitation energies. We examine how the frequency position, intensity and lineshape of the main Raman modes (A11g, E2g, and A21g) behave by the variation of the layer thickness and excitation energy. We observed a frequency dispersion on the number of layers of the main modes, indicating changes in the inter- and intra-layers interaction. A resonant Raman condition is reached for all modes for samples with 11 and 18 nm thickness because of van Hove singularities at the electronic density of states. Also, the Breit-Wigner-Fano line shape of the A21g mode shows an increase of electron-phonon coupling for thick layers. These results suggest a relevant influence of numbers of layers on the Raman scattering mechanics in Bi2Te3 systems.

Modeling Photolytic Decomposition of Energetically Functionalized Dodecanes.

The photolytic stability of explosives and energetic functional groups is of importance for those who regularly handle or are exposed to explosives in typical environmental conditions. This study models the photolytic degradation of dodecane substituted with various energetic functional groups: azide, nitro, nitrate ester, and nitramine. For the studied molecules, it was found that excitons localize on the energetic functional group, no matter where they were initially formed, and thus, the predominant degradation pathway involves the degradation of the energetic functional group. The relative trends for both 4 and 8 eV excitation energies followed with what is expected from the relative stability of the energetic functional groups to thermal and sub-shock degradation. The one notable exception was the azide functional group; more work should be done to further understand the photolytic effects on the azide functional group.

Raman scattering with infrared excitation resonant with the MoSe2 indirect band gap

Resonance Raman scattering, which probes electrons, phonons, and their interplay in crystals, is extensively used in two-dimensional materials. Here we investigate Raman modes in $\mathrm{MoSe}_{2}$ at different laser excitation energies from 2.33 eV down to the near infrared 1.16 eV. The Raman spectrum at 1.16 eV excitation energy shows that the intensity of high-order modes is strongly enhanced if compared to the first-order phonon modes' intensity due to resonance effects with the $\mathrm{MoSe}_{2}$ indirect band gap. By comparing the experimental results with the two-phonon density of states calculated with density functional theory, we show that the high-order modes originate mostly from two-phonon modes with opposite momenta. In particular, we identify the momenta of the phonon modes that couple strongly with the electrons to produce the resonance process at 1.16 eV, while we verify that at 2.33 eV the two-phonon modes' line shape compares well with the two-phonon density of states calculated over the entire Brillouin zone. We also show that by lowering the crystal temperature, we actively suppress the intensity of the resonant two-phonon modes and we interpret this as the result of the increase of the indirect band gap at low temperature that moves our excitation energy out of the resonance condition.

Band Gap Control and Properties of Indium–Zinc Oxynitride Thin Films Grown by Molecular Beam Epitaxy

The material system of II–III oxynitride semiconductors has opened new prospects in solar energy harvesting and photocatalysis in recent years due to a tunable band gap and favorable band edge positions with respect to important redox levels. A promising member of this family is In–Zn–O–N (IZNO), as its band gap can be tailored to lower values compared to its better studied cousin Ga–Zn–O–N. We study IZNO thin films grown on sapphire substrates by molecular beam epitaxy (MBE) and investigate their structural, surface morphology, optical absorption, and photoemission characteristics. We investigate the influence of the constituting elements in the alloy on the position of valence band maxima, conduction band minima, and the structural properties. Through precise variation of the composition, samples with a band gap range between 1.0 and 2.6 eV have been deposited and analyzed. Based on our results, Zn and N have been identified to lower the energy of valence and conduction band edges with respect to the vacuum level, while In and O have the opposite effect. Structural characterization reveals that the samples are polycrystalline with grain sizes of about 30 nm, comprising a mixture of cubic and hexagonal crystal phases with distinct short-range disorder. While in the ternary compounds In–O–N and Zn–O–N metal–oxide bonds are dominant, we elucidate the formation of metal–oxynitride bonds in IZNO. Electrical and optical measurements reveal charge carrier concentrations of 1018–1020 cm–3 and absorption coefficients of 105 cm–1 above about 2 eV excitation energy, accompanied by pronounced free carrier absorption found in samples in the upper carrier concentration range in the infrared energy region. Typical Urbach energies are 80–220 meV, with no clear correlation with the elemental composition. By introducing MBE growth for IZNO, we overcome the limitations typically inflicted by the fabrication methods on stoichiometric InN:ZnO solid solutions and provide unprecedented access to new compounds in this material class.

Ultrafast Charge-Transfer Dynamics in Twisted MoS2/WSe2 Heterostructures.

Two-dimensional transition metal dichalcogenides offer a fascinating platform for creating van der Waals heterojunctions with exciting physical properties. Because of their typical type-II band alignment, photoexcited electrons and holes can separate via interfacial charge transfer. Furthermore, the relative crystallographic alignment of the individual layers in these heterostructures represents an important degree of freedom. Based on both effects, various fascinating ideas for applications in optoelectronics and valleytronics have been suggested. Despite its utmost importance for the design and efficiency of potential devices, the nature and the dynamics of ultrafast charge transfer are not yet well understood. This is mainly because the charge transfer can be surprisingly fast, usually faster than the temporal resolution of previous experimental approaches. Here, we apply time- and polarization-resolved second-harmonic imaging microscopy to investigate the charge-transfer dynamics for three MoS2/WSe2 heterostructures with different stacking angles at a previously unattainable time resolution of ≈10 fs. For 1.70 eV excitation energy, electron transfer from WSe2 to MoS2 is found to depend considerably on the stacking angle with the fastest transfer time observed to be as short as 12 fs. At 1.85 eV excitation energy, ultrafast hole transfer from MoS2 to hybridized states at the Γ-point and to the K-points of WSe2 has to be considered. Surprisingly, the corresponding decay dynamics show only a minor stacking-angle dependence indicating that radiative recombination of momentum-space indirect Γ-K excitons becomes the dominant decay route for all samples.

Oxygen-redox reactions in LiCoO2 cathode without O–O bonding during charge-discharge

Summary Oxygen activity in highly delithiated LiCoO2 is critical to fully utilizing the energy density of this high-tap-density cathode but still lacks a clear understanding. In this work, we combined the results of several experimental techniques, especially resonant inelastic X-ray scattering (RIXS) and neutron pair distribution function (NPDF) analysis, together with theoretical calculations to study this topic. Our results conclude that oxygen redox takes place globally in the lattice, rather than forming localized dimerization as previously thought. RIXS results directly reveal the reversible oxygen redox, and NPDF results show that the O–O pair distance is considerably shortened in the highly delithiated LiCoO2. Theoretical calculations indicate that no O–O bonding is formed in LiCoO2, in sharp contrast to the lithium-rich system in which O–O bonding does form. These results provide the rationale for achieving a reversible deep delithiation and high energy density for LiCoO2-based electrodes.

Subauroral Green STEVE Arcs: Evidence for Low‐Energy Excitation

AbstractSubauroral emissions known as STEVEs (Strong Thermal Emission Velocity Enhancements) are sometimes accompanied by green arcs containing magnetic field‐aligned “picket fence” structures. In a newly published spectrum of a green picket fence arc Gillies et al. (2019, https://doi.org/10.1029/2019GL083272) showed that the visible emission in such arcs is mostly OI 557.7 nm with minimal N2+ 1N. This finding is consistent with the color ratios found in digital camera photos (Mende & Turner, 2019, https://doi.org/10.1029/2019JA026851) and is distinct from the ratios in auroral precipitation. The spectrum also contains intense N2 first positive (1P) emission. The presence of OI 557.7 (~4.19 eV excitation energy) and N2 1P (~7.35 eV), combined with the lack of N2+ first negative (~18.75 eV) commonly seen in the aurora, suggests that the particles exciting the emission have energy <18.75 eV. This is strong evidence against the precipitation hypothesis recently put forth (Nishimura et al., 2019, https://doi.org/10.1029/2019GL082460; Gillies et al., 2019, https://doi.org/10.1029/2019GL083272).

Raman scattering investigation of the electron-phonon coupling in superconducting Nd(O,F)BiS2

We have performed polarized Raman scattering measurements on the newly discovered superconductor Nd(O,F)BiS$_2$ ($T_c = 4$ K). We observe 2 Raman active modes, with frequencies in accordance with first-principles calculations. One A$_{1g}$ phonon mode at 112.4 cm$^{-1}$ exhibits a Fano line shape due to electron-phonon coupling. We find a resonance for this mode at 2.45 eV excitation energy. We estimate a 0.68 contribution of this mode to the electron-phonon coupling constant $\lambda$. Our Raman results suggest that the BiS$_2$-based superconductors are possibly phonon-mediated BCS superconductors.

A simplified Tamm-Dancoff density functional approach for the electronic excitation spectra of very large molecules

Two approximations in the Tamm-Dancoff density functional theory approach (TDA-DFT) to electronically excited states are proposed which allow routine computations for electronic ultraviolet (UV)- or circular dichroism (CD) spectra of molecules with 500-1000 atoms. Speed-ups compared to conventional time-dependent DFT (TD-DFT) treatments of about two to three orders of magnitude in the excited state part at only minor loss of accuracy are obtained. The method termed sTDA ("s" for simplified) employs atom-centered Löwdin-monopole based two-electron repulsion integrals with the asymptotically correct 1∕R behavior and perturbative single excitation configuration selection. It is formulated generally for any standard global hybrid density functional with given Fock-exchange mixing parameter ax. The method performs well for two standard benchmark sets of vertical singlet-singlet excitations for values of ax in the range 0.2-0.6. The mean absolute deviations from reference data are only 0.2-0.3 eV and similar to those from standard TD-DFT. In three cases (two dyes and one polypeptide), good mutual agreement between the electronic spectra (up to 10-11 eV excitation energy) from the sTDA method and those from TD(A)-DFT is obtained. The computed UV- and CD-spectra of a few typical systems (e.g., C60, two transition metal complexes, [7]helicene, polyalanine, a supramolecular aggregate with 483 atoms and about 7000 basis functions) compare well with corresponding experimental data. The method is proposed together with medium-sized double- or triple-zeta type atomic-orbital basis sets as a quantum chemical tool to investigate the spectra of huge molecular systems at a reliable DFT level.

HST-COS OBSERVATIONS OF AGNs. I. ULTRAVIOLET COMPOSITE SPECTRA OF THE IONIZING CONTINUUM AND EMISSION LINES

The ionizing fluxes from quasars and other active galactic nuclei (AGN) are critical for interpreting the emission-line spectra of AGN and for photoionization and heating of the intergalactic medium. Using ultraviolet spectra from the Cosmic Origins Spectrograph (COS) on the Hubble Space Telescope (HST), we have directly measured the rest-frame ionizing continua and emission lines for 22 AGN. Over the redshift range 0.026 < z < 1.44, COS samples the Lyman continuum and many far-UV emission lines (Lya 1216, C IV 1549, Si IV/OIV] 1400, N V 1240, O VI 1035). Strong EUV emission lines with 14-22 eV excitation energies (Ne VIII 770,780, Ne V 569, O II 834, O III 833, 702, O IV 788,608,554, O V 630, N III 685) suggest the presence of hot gas in the broad emission-line region. The rest-frame continuum, F_nu ~ nu^{alpha_nu}, shows a break at wavelengths below 1000 A, with spectral index alpha_nu = -0.68 +/- 0.14 in the FUV (1200-2000 A) steepening to alpha_nu = -1.41 +/- 0.21 in the EUV (500-1000 A). The COS EUV index is similar to that of radio-quiet AGN in the 2002 HST/FOS survey (alpha_nu = -1.57 +/- 0.17). We see no Lyman edge (tau_HI < 0.03) or He I 584 emission in the AGN composite. Our 22 AGN exhibit a substantial range of FUV/EUV spectral indices and a correlation with AGN luminosity and redshift, likely due to observing below the 1000 A break.

Photoelectron spectroscopy of higher bromine and iodine oxide anions: Electron affinities and electronic structures of BrO2,3 and IO2–4 radicals

This report details a photoelectron spectroscopy (PES) and theoretical investigation of electron affinities (EAs) and electronic structures of several atmospherically relevant higher bromine and iodine oxide molecules in the gas phase. PES spectra of BrO(2)(-) and IO(2)(-) were recorded at 12 K and four photon energies--355 nm/3.496 eV, 266 nm/4.661 eV, 193 nm/6.424 eV, and 157 nm/7.867 eV--while BrO(3)(-), IO(3)(-), and IO(4)(-) were only studied at 193 and 157 nm due to their expected high electron binding energies. Spectral features corresponding to transitions from the anionic ground state to the ground and excited states of the neutral are unraveled and resolved for each species. The EAs of these bromine and iodine oxides are experimentally determined for the first time (except for IO(2)) to be 2.515 ± 0.010 (BrO(2)), 2.575 ± 0.010 (IO(2)), 4.60 ± 0.05 (BrO(3)), 4.70 ± 0.05 (IO(3)), and 6.05 ± 0.05 eV (IO(4)). Three low-lying excited states along with their respective excitation energies are obtained for BrO(2) [1.69 (A (2)B(2)), 1.79 (B (2)A(1)), 1.99 eV (C (2)A(2))], BrO(3) [0.7 (A (2)A(2)), 1.6 (B (2)E), 3.1 eV (C (2)E)], and IO(3) [0.60 (A (2)A(2)), 1.20 (B (2)E), ∼3.0 eV (C (2)E)], whereas six excited states of IO(2) are determined along with their respective excitation energies of 1.63 (A (2)B(2)), 1.73 (B (2)A(1)), 1.83 (C (2)A(2)), 4.23 (D (2)A(1)), 4.63 (E (2)B(2)), and 5.23 eV (F (2)B(1)). Periodate (IO(4)(-)) possesses a very high electron binding energy. Only one excited state feature with 0.95 eV excitation energy is shown in the 157 nm spectrum. Accompanying theoretical calculations reveal structural changes from the anions to the neutrals, and the calculated EAs are in good agreement with experimentally determined values. Franck-Condon factors simulations nicely reproduce the observed vibrational progressions for BrO(2) and IO(2). The low-lying excited state information is compared with theoretical calculations and discussed with their atmospheric implications.

Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy

The double bond photoisomerization of fulvene has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method. Fulvene is a test case to develop optical control strategies based on the knowledge of the excited state decay mechanism. The decay takes place on a time scale of several hundred femtoseconds, and the potential energy surface is centered around a conical intersection seam between the ground and excited state. The competition between unreactive decay and photoisomerization depends on the region of the seam accessed during the decay. The dynamics are carried out on a four-dimensional model surface, parametrized from complete active space self-consistent field calculations, that captures the main features of the seam (energy and locus of the seam and associated branching space vectors). Wave packet propagations initiated by single laser pulses of 5-25 fs duration and 1.85-4 eV excitation energy show the principal characteristics of the first 150 fs of the photodynamics. Initially, the excitation energy is transferred to a bond stretching mode that leads the wave packet to the seam, inducing the regeneration of the reactant. The photoisomerization starts after the vibrational energy has flowed from the bond stretching to the torsional mode. In our propagations, intramolecular energy redistribution (IVR) is accelerated for higher excess energies along the bond stretch mode. Thus, the competition between unreactive decay and isomerization depends on the rate of IVR between the bond stretch and torsion coordinates, which in turn depends on the excitation energy. These results set the ground for the development of future optical control strategies.

Femtosecond relaxation kinetics of highly excited $\mathrm{M}_{\mathrm{Na}}^{**}$ states in CaF2 at 3.2 eV and 4.7 eV

Femtosecond (fs) laser pulses at variable delay times allowed us to track the fast non-radiative transitions between the manifold of highly excited \(\mathrm{M}_{\mathrm{Na}}^{**}\) states to the lower lying fluorescent \(\mathrm{M}_{\mathrm{Na}}^{*}\) state in CaF2. Two distinct \(\mathrm{M}_{\mathrm{Na}}^{**}\) states of the manifold at 3.16 eV (\(\mathrm{M}_{\mathrm{Na}2}^{**}\)) and 4.73 eV (\(\mathrm{M}_{\mathrm{Na}3}^{**}\)) were populated using the second (SH) and third harmonics (TH) of fs laser light at 785 nm. The population kinetics of the fluorescent \(\mathrm{M}_{\mathrm{Na}}^{*}\) state in the 2 eV excitation energy range was revealed by depleting its fluorescence centered at 740 nm using fundamental near infrared (NIR) fs laser pulses. The related time constants for \(\mathrm{M}_{\mathrm{Na}2,3}^{**}{\sim}{>} \mathrm{M}_{\mathrm{Na}}^{*}\) relaxation amounted to 1.0±0.14 ps and 3.0±0.3 ps upon SH and TH excitation, respectively.

State-resolved investigation of the photodesorption dynamics of NO from (NO)2 on Ag nanoparticles of various sizes in comparison with Ag(111)

The translational and internal state energy distributions of NO desorbed by laser light (2.3, 3.5, and 4.7 eV) from adsorbed (NO)(2) on Ag nanoparticles (NPs) (mean diameters, D = 4, 8, and 11 nm) have been investigated by the (1 + 1) resonance enhanced multiphoton ionization technique. For comparison, the same experiments have also been carried out on Ag(111). Detected NO molecules are hyperthermally fast and both rotationally and vibrationally hot, with temperatures well above the sample temperature. The translational and rotational excitations are positively correlated, while the vibrational excitation is decoupled from the other two degrees of freedom. Most of the energy content of the desorbing NO is contained in its translation. The translational and internal energy distributions of NO molecules photodesorbed by 2.3, 3.5, and in part also 4.7 eV light are approximately constant as a function of Ag NPs sizes, and they are the same on Ag(111). This suggests that for these excitations a common mechanism is operative on the bulk single crystal and on NPs, independent of the size regime. Notably, despite the strongly enhanced cross section seen on NP at 3.5 eV excitation energy in p-polarization, i.e., in resonance with the plasmon excitation, the mechanism is also unchanged. At 4.7 eV and for small particles, however, an additional desorption channel is observed which results in desorbates with higher energies in all degrees of freedom. The results are well compatible with our earlier measurements of size-dependent translational energy distributions. We suggest that the broadly constant mechanism over most of the investigated range runs via a transient negative ion state, while at high excitation energy and for small particles the transient state is suggested to be a positive ion.

Doping dependence of the Raman peaks intensity of graphene close to the Dirac point

Here we use pristine graphene samples in order to analyze how the Raman peaks intensity, measured at 2.4 eV and 1.96 eV excitation energy, changes with the amount of doping. The use of pristine graphene allows investigating the intensity dependence close to the Dirac point. We show that the G peak intensity is independent on the doping, while the 2D peak intensity strongly decreases for increasing doping. Analyzing this dependence in the framework of a fully resonant process, we found that the total electron-phonon scattering rate is ~40 meV at 2.4 eV.

Resonant Inelastic X-ray Scattering study of H2S molecules around the sulfur K absorption edge

Resonant Inelastic X-ray Scattering (RIXS) measurements were performed on H2S molecules with excitation energy tuned around the 1s ionization threshold of sulfur. A Johansson type crystal spectrometer was employed to record a series of resonant Kα (1s→2p transition) and Kβ (1s→3p transition) x-ray spectra in the 2469–2489 eV excitation energy range building a full 2D scattering plane. Ultrafast nuclear dynamics have been observed in the RIXS H2S spectra measured after excitation along the dissociative resonance around 2472 eV.

Matrix effect of aluminium, calcium and magnesium in axially viewing inductively coupled plasma atomic emission spectrometry

The matrix effect due to Al, Ca and Mg in axial view mode ICP-AES was investigated over analyte lines with total excitation energy from 1.62 to 16.51 eV. A global qualitative explanation of the action of the matrix is proposed. The energy is directly transferred between matrix and analyte specimens (atoms or ions) during inelastic collisions, which are particularly relevant in the 1.62–8 eV excitation energy range, where the direct action with argon specimens is less probable to occur. Concrete applications of this global qualitative explanation are given, taking into account the resonance energy effect and the spin conservation rule. The characteristic matrix effect of Al and Ca for lines excited by charge transference mechanism was observed. In the presence of Mg, other possible matrix–analyte interactions may reduce the efficiency of this mechanism. The particular behavior of the matrix effect for lines in the 10.5–11.5 eV energy range can be considered as experimental evidence of the Penning ionization–excitation mechanism, which probably actuates along other matrix–analyte interactions.

Conical intersections and strong nonadiabatic coupling effects in singlet-excited acetylene: An ab initio quantum dynamical study

The conically intersecting potential energy surfaces of the S 1 and S 2 excited states of acetylene and the resulting strong nonadiabatic couplings are investigated theoretically. The adiabatic potential energy surfaces are obtained from high-level MRCI calculations. They are diabatized using the concept of regularized diabatic states and then used as a basis for the subsequent wave-packet dynamical treatment of the nuclear motion. All three angular degrees of freedom are included in the present study, while the bond lengths are kept frozen. The importance of the nonadiabatic interactions for the fine structure of the VUV spectrum of acetylene in the 6.5–8 eV excitation energy range is established. The electronic populations display an S 2 → S 1 internal conversion process on the order of 50 fs, which is, however, incomplete owing to the relatively small S 2–S 1 energy gap and the present reduced-dimensionality treatment. Snapshots of the wave-packet as well as angular probability densities are analyzed and reveal, for the first time, an incipient excited-state cis–trans isomerization in this system.