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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

How Does Bending the Uranyl Unit Influence Its Spectroscopy and Luminescence?

We report bent uranyl complexes can be formed with chloride ligands and 1,10-phenanthroline (phen) ligands bound to the equatorial and axial planes of the uranyl(VI) moiety, as revealed by the crystal structures, IR and Raman spectroscopy, and quantum-chemical calculations. With the goal of probing the influence of chloride and phenanthroline coordination enforcing the bending on the absorption and emission spectra of this complex, spin–orbit time-dependent density functional theory calculations for the bare uranyl complexes as well as for the free UO 2 Cl 2 subunit and the UO 2 Cl 2 (phen) 2 complex were performed. The emission spectra have been fully simulated by ab initio methods and compared to experimental photoluminescence spectra, recorded for the first time for UO 2 Cl 2 (phen) 2 . Notably, the bending of uranyl in UO2Cl2 and UO 2 Cl 2 (phen) 2 triggers excitations of the uranyl bending mode, yielding a denser luminescence spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Practical Guide to Chemometric Analysis of Optical Spectroscopic Data

The methodology and mathematical treatment of several classic multivariate methods for the analysis of spectroscopic data is demonstrated in a straightforward way that can be used as a basis for teaching an undergraduate introductory course on chemometric analysis. The multivariate techniques of classical least squares (CLS), principal component regression (PCR), and partial least squares (PLS), as well as the univariate Beer’s law method have been described and compared, building students’ understanding by starting with the univariate method and progressing step by step into the multivariate methods. Equations for the production of regression vectors from training set spectral data is described and their use demonstrated for the prediction of constituent concentrations on a separate validation set of spectra. Extreme care is taken to ensure consistency in variable formatting of data matrices. This provides a key foundation to understanding how spectral data are manipulated using these different mathematical approaches for building quantitative regression models. Each method is applied to a real-world data set, and the results are discussed to show students the types of information that can be gleaned from each method. A training set comprised of 20 infrared absorbance spectra containing 3 constituents (benzene, polystyrene, and gasoline) of known composition are used to demonstrate the matrix operations for each regression method. A separate set of 12 real-world napalm samples (containing benzene, polystyrene and gasoline) are used as a validation set to demonstrate the ability to utilize the regression models on an unknown dataset. A toolbox (PNNL Chemometric Toolbox) written in MATLAB language is supplied in the Supplemental Information file and can be used as a companion for understanding the development and deployment of the chemometric algorithms described in this paper. The datasets of the infrared spectra are also supplied, allowing users to build and inspect the chemometric models on their own. Finally, the Toolbox includes scripts to assist users in loading their own datasets into MATLAB and performing CLS, PCR, and PLS on their data.

Upper-Division Undergraduate, Analytical Chemistry↗
DOE OSTI2024

Sparse-Stochastic Fragmented Exchange for Large-Scale Hybrid Time-Dependent Density Functional Theory Calculations

Here we extend our recently developed sparse-stochastic fragmented exchange formalism for ground-state near-gap hybrid DFT to calculate absorption spectra within linear-response time-dependent generalized Kohn-Sham DFT (LR-GKS-TDDFT) for systems consisting of thousands of valence electrons within a grid-based/plane-wave representation. A mixed deterministic/fragmented-stochastic compression of the exchange kernel, here using long-range explicit exchange functionals, provides an efficient method for accurate optical spectra. Both real-time propagation as well as frequency-resolved Casida-equation-type approaches for spectra are presented, and the method is applied to large molecular dyes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Velocity-Map Imaging and Magnetic-Bottle Photoelectron Spectroscopy of [SeCCH] – : Electronic Properties and Spin–Orbit Splitting

In this work, the recently synthesized acetylide compound KSeCCH containing the main group element selenium within the novel and in crystalline form unprecedented [SeCCH] – anion was successfully investigated in the gas phase by high-resolution velocity-map imaging (VMI) and magnetic-bottle (MB) photoelectron spectroscopy coupled with an electrospray ionization source. Both VMI and MB spectra exhibited identical electron affinities (EA, 2.517 ± 0.002 eV), spin–orbit coupling (SOC) splittings (1492 ± 20 cm –1 ), and Se–C stretching frequencies (573 ± 20 cm –1 ) of the corresponding neutral tetra-atomic radical [SeCCH] • with the VMI spectrum possessing six times higher spectral resolution compared with the MB spectrum. These experimental values were well reproduced by calculations at the CCSD(T) level, in which both the isolated [SeCCH] – anion and the [SeCCH] • radical adopted linear geometries. The simulated spectra based on the calculated Franck–Condon factors, the SOC splitting, and the experimental line width matched well with the measured spectra. Furthermore, comparisons of the EA and SOC splitting values with the previously reported isolobal species [SeCN] • are also made and discussed. The decrease in the EA and SOC splitting of [SeCCH] • is ascribed to the differences in the electronegativities between C and N atoms as well as the electron density on the Se atom in its singly occupied molecular orbital (SOMO).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photoionization of C 4 H 5 Isomers

In this work, single-photon, photoelectron–photoion coincidence spectroscopy is used to record the mass-selected ion spectra and slow photoelectron spectra of C 4 H 5 radicals produced by the abstraction of hydrogen atoms from three C 4 H 6 precursors by fluorine atoms generated by a microwave discharge. Three different C 4 H 5 isomers are identified, with the relative abundances depending on the nature of the precursor (1-butyne, 1,2-butadiene, and 1,3-butadiene). The results are compared with our previous work using 2-butyne as a precursor [ Hrodmarsson, H. R. J. Phys. Chem. A 2019 , 123 , 1521-1528]. The slow photoelectron spectra provide new information on the three radical isomers that is in good agreement with previous experimental and theoretical results [ Lang, M. J. Phys. Chem. A 2015 , 119 , 3995-4000; Hansen, N. J. Phys. Chem. A 2006 , 110 , 3670–3678]. The energy scans of the C 4 H 5 photoionization signal are recorded with substantially better resolution and signal-to-noise ratio than those in earlier work, allowing the observation of autoionizing resonances based on excited states of the C 4 H 5 cation. Photoelectron images recorded at several energies are also reported, providing insight into the decay processes of these excited states. Finally, in contrast to the earlier work using 2-butyne as a precursor, where H-atom abstraction was the only observed process, F- and H-atom additions to the present precursors are also observed through the detection of C 4 H 6 F, C 4 H 5 F, and C 4 H 7

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Interplay of Open-Shell Spin-Coupling and Jahn–Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

Here we report a theoretical investigation and elucidation of the X-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization and the measurement of the carbon K-edge spectra of both species using a table-top high-harmonic generation source are described in the companion experimental paper. We show that the 1sC → π transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence of the unpaired (spectator) electron in the π-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC → π* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation. The prominent split structure of the 1sC → π* band of the cation is attributed to the interplay between the coupling of the core → π* excitation with the unpaired electron in the π-subshell and the Jahn–Teller distortion. The calculations attribute most of the splitting (~1–1.2 eV) to the spin coupling, which is visible already at the Franck–Condon structure, and we estimate the additional splitting due to structural relaxation to be around ~0.1–0.2 eV. These results suggest that X-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn–Teller effect in the benzene cation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Metal-to-Ligand Charge-Transfer Spectrum of a Ru-Bipyridine-Sensitized TiO 2 Cluster from Embedded Multiconfigurational Excited-State Theory

Understanding optical properties of the dye molecule in dye-sensitized solar cells (DSSCs) from first-principles quantum mechanics can contribute to improving the efficiency of such devices. While density functional theory (DFT) and time-dependent DFT have been pivotal in simulating optoelectronic properties of photoanodes used in DSSCs at the atomic scale, questions remain regarding DFT’s adequacy and accuracy to furnish critical information needed to understand the various excited-state processes involved. In this work, we simulate the absorption spectra of a dye-sensitized solar cell analogue, comprised of a Ru-bipyridine (Ru-bpy) dye molecule and a small TiO2 cluster via DFT and via an accurate embedded correlated wavefunction (CW) theory. We generated CW spectra for the adsorbed Ru-bpy dye via a recently introduced capped density functional embedding theory or capped-DFET (to generate the embedding potential that accounts for the interaction of the molecule and the TiO 2 cluster). We then combined capped-DFET with the accurate but expensive multiconfigurational complete active space second-order perturbation theory (CASPT2)—embedded CASPT2. Because the CW theory is conducted on only a portion of the total system in the presence of an embedding potential that describes that portion’s interaction with its environment, we efficiently obtain CW-quality predictions that reflect local properties of the entire system. Specifically, for example, with capped-DFET and embedded CW theory, we can simulate accurately a plethora of metal-to-ligand charge-transfer excited properties at a manageable computational cost. Here, we predict detailed electronic spectra within the visible region, featuring the lowest three singlet and triplet excited states, along with predictions of the singlets’ lifetimes. We illustrated these results using a Jablonski diagram that show the relative energy position of the singlet and longer-lived triplet excited states and analyzed and proposed relaxation paths for the excited state corresponding to the most intense but short-lived absorption (interconversion, intersystem crossing, fluorescence, and phosphorescence) that may lead to longer-lived excited states necessary for efficient charge separation required to generate current in solar cells.

14 SOLAR ENERGY↗
DOE OSTI2021

Pulse Radiolysis Investigation of Radicals Derived from Water-Soluble Cyanine Dyes: Implications for Super-resolution Microscopy

Light-induced blinking, an inherent feature of many forms of super-resolution microscopy, has been linked to transient reduction of the fluorescent cyanine dye used as an imaging agent. There is, however, only scant literature information related to one-electron reduced cyanine dyes, especially in an aqueous environment. Here, we examine a small series of cyanine dyes, possessing disparate π-conjugation lengths, under selective reducing or oxidizing conditions. The experiment allows recording of both differential absorption spectra and decay kinetics of the resultant one-electron reduced or oxidized transient species in water. Relative to the ground state, absorption transitions for the various radicals are weak and somewhat broadened but do allow correlation with the π-conjugation length. In all cases, absorption maxima lie to the blue of the main ground-state transition. Under anaerobic conditions, the transient species decay on the microsecond to millisecond time scale, with the mean lifetime depending on molecular structure, radiation dose, and dye concentration. The experimental absorption spectra recorded for the one-electron reduced radicals and the presumed dimer cation radical compare well to spectra obtained from time-dependent density functional theory calculations. Furthermore, the results allow conclusions to be drawn regarding the plausibility of the reduced species being responsible for light-induced blinking in direct stochastic optical reconstruction microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Two-Color IRMPD Applied to Conformationally Complex Ions: Probing Cold Ion Structure and Hot Ion Unfolding

Two-color infrared multiphoton dissociation (2C-IRMPD) spectroscopy is a technique that mitigates spectral distortions due to nonlinear absorption that is inherent to one-color IRMPD. We use a 2C-IRMPD scheme that incorporates two independently tunable IR sources, providing considerable control over the internal energy content and type of spectrum obtained by varying the trap temperature, the time delays and fluences of the two infrared lasers, and whether the first or second laser wavelength is scanned. In this work, we describe the application of this variant of 2C-IRMPD to conformationally complex peptide ions. The 2C-IRMPD technique is used to record near-linear action spectra of both cations and anions with temperatures ranging from 10 to 300 K. In this work, we also determine the conditions under which it is possible to record IR spectra of single conformers in a conformational mixture. Furthermore, we demonstrate the capability of the technique to explore conformational unfolding by recording IR spectra with widely varying internal energy in the ion. The protonated peptide ions YGGFL (NH 3 + -Tyr-Gly-Gly-Phe-Leu, Leu-enkephalin) and YGPAA (NH 3 + -Tyr-Gly-Pro-Ala-Ala) are used as model systems for exploring the advantages and disadvantages of the method when applied to conformationally complex ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Identity and Chemistry of C 7 H 7 Radicals Observed during Soot Formation

Here we used aerosol mass spectrometry coupled with tunable synchrotron photoionization to measure radical and closed-shell species associated with particle formation in premixed flames and during pyrolysis of butane, ethylene, and methane. We analyzed photoionization (PI) spectra for the C 7 H 7 radical to identify the isomers present during particle formation. For the combustion and pyrolysis of all three fuels, the PI spectra can be fit reasonably well with contributions from four radical isomers: benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl. Although there are significant experimental uncertainties in the isomeric speciation of C7H 7 , the results clearly demonstrate that the isomeric composition of C 7 H 7 strongly depends on the combustion or pyrolysis conditions and the fuel or precursors. Fits to the PI spectra using reference curves for these isomers suggest that all of these isomers may contribute to m/z 91 in butane and methane flames, but only benzyl and vinylcyclopentadienyl contribute to the C 7 H 7 isomer signal in the ethylene flame. Only tropyl and benzyl appear to play a role during pyrolytic particle formation from ethylene, and only tropyl, vinylcyclopentadienyl, and o-tolyl appear to participate during particle formation from butane pyrolysis. There also seems to be a contribution from an isomer with an ionization energy below 7.5 eV for the flames but not for the pyrolysis conditions. Kinetic models with updated and new reactions and rate coefficients for the C 7 H 7 reaction network predict benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl to be the primary C 7 H 7 isomers and predict negligible contributions from other C 7 H 7 isomers. These updated models provide better agreement with the measurements than the original versions of the models but, nonetheless, underpredict the relative concentrations of tropyl, vinylcyclopentadienyl, and o-tolyl in both flames and pyrolysis and overpredict benzyl in pyrolysis. Our results suggest that there are additional important formation pathways for the vinylcyclopentadienyl, tropyl, and o-tolyl radicals and/or loss pathways for the benzyl radical that are currently unaccounted for in the present models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

High-Resolution Photoelectron Spectroscopy of NO3 – Vibrationally Excited Along Its ν3 Mode

The nitrate (NO3) radical has long been the subject of both experimental and theoretical studies due to its complex electronic structure resulting from vibronic interactions between its X̃2A2' and B̃2E' states. In particular, the definite assignment of the fundamental of its degenerate stretching vibration (ν3) is still under debate. Here, we report high-resolution photoelectron spectra of vibrationally pre-excited NO3- using the recently developed IR-cryo-SEVI technique. The anions are excited through infrared (IR) excitation near 1350 cm-1, accessing the ν3 and 2ν3(e') vibrational levels with band centers at 1350.5 and ∼2700 cm-1, respectively. The IR-cryo-SEVI spectrum for 2ν3 pre-excitation shows clear evidence for an intense 321 transition. From the position of this feature (30031 cm-1), the electron affinity of NO3 also determined in this work (31680 cm-1), and the IR excitation energy, we obtain a fundamental frequency of 1051 cm-1 for the ν3 fundamental of the NO3 radical. This assignment and other features in the IR-cryo-SEVI spectra are supported by spectral simulations based on a vibronic Köppel-Domcke-Cederbaum Hamiltonian. The simulations also show that nearly all features in the IR-cryo-SEVI spectra arise because of pseudo-Jahn-Teller coupling between the X̃ and B̃ states of NO3. The results and analysis presented here settle a long-standing controversy regarding the ν3 frequency of NO3.

Anions↗
DOE OSTI2025

An Experimental and Theoretical Study of the Valence Shell Electronic Structure of Nitromethane

Vibrationally resolved CH 3 NO 2 and CD 3 NO 2 photoelectron spectra and angular distribution parameters, β, have been measured in the photon energy range 20–80 eV. This allows a comprehensive investigation of conflicting literature interpretations of the two outermost photoelectron bands, complemented by high-level calculations characterizing the three O lone-pair-based orbital ionizations expected in this region. Franck–Condon simulations allow the regular vibrational progressions observed at the beginning of the first and second bands to be assigned as predominantly modes v 5 and v 6 of the D 0 and D 2 cation states, respectively. Irregular structuring observed midband in both bands is attributed to avoided crossings between the adiabatic D 0 /D 1 and D 1 /D 2 states as identified in potential surface cuts taken along the v 5 and v 6 normal mode coordinates. The associated D 0 /D 1 and D 1 /D 2 conical intersections were located and characterized, allowing possible vibronic coupling and its impact on the photoelectron spectra of the D 0 , D 1 , and D 2 states to be discussed. This helps rationalize the apparently missing D 1 ionization in this region, although some contribution by this state may be identifiable in the β-parameter spectra. Theoretical analysis of the complete valence region spectrum identifies the early breakdown of the independent electron model beyond these first two bands.

Powis, Ivan [University of Nottingham (United King↗
DOE OSTI2026

Fingerprinting Uranium Oxides with Electron Energy Loss Spectroscopy Supported by Theoretical Computations

Uranium oxides occur in a variety of phases that differ in crystal structure and uranium oxidation states. Electron energy loss spectroscopy (EELS) is one of the few techniques that has sufficient spatial resolution and sensitivity to electronic structure to distinguish amongst phases at the nanoscale. However, beam-sensitive materials such as uranium oxides are subject to spectral modification due to interactions with the electron beam. Therefore, theory support is essential to reliably exclude the impact of beam damage and generate true reference datasets. Here we use a comparison of theoretical and experimental spectra to probe the impact of beam damage on O K-edge and U N-edge (N6,7 and N4,5) EELS spectra of various single-valent and mixed-valence uranium oxide bulk phases. Using a low-dose experimental set-up, we show that the O K-edge theoretical spectra are in excellent agreement with experiment for both peak positions and relative intensities of respective peaks. In contrast, U N-edge features are less distinguishing due to the partially localized nature of the U 5f orbitals and overlapping multiplet and spin–orbit coupling effects. This work demonstrates that O K-edge EELS is sufficiently diagnostic to distinguish a wide range of uranium oxides and that the experimental approach used here minimizes beam damage and allows valence state discrimination across the U(IV), U(V) and U(VI) series. When combined with imaging modes available in electron mi-croscopy, the work enables detailed investigation and characterization of uranium redox transformations at the nanoscale.

Carbone, Jacopo↗
DOE OSTI2020

On the Red Antenna States of Photosystem I Mutants from Cyanobacteria Synechocystis PCC 6803

To identify the molecular composition of the low-energy states in cyanobacterial Photosystem I (PSI) of Synechocystis PCC6803, we focus on high resolution (low-temperature) absorption, emission, resonant, and nonresonant hole burned spectra obtained for wild-type (WT) PSI and three PSI mutants. In the Red_a mutant, the B33 chlorophyll (Chl) is added to the B31-B32 dimer; in Red_b, histidine 95 (His95) on PsaB (which coordinates Mg in the B7 Chl within the His95-B7-A31-A32- cluster) is replaced with glutamine (Gln), while in the Red_ab mutant, both mutations are made. We show that the C706 state (B31-B32) changes to the C710 state (B31-B32-B33) in both Red_a and Red_ab mutants, while the C707 state in WT Synechocystis (localized on the His95-B7-A31-A32 cluster) is modified to C716 in both Red_b and Red_ab. Excitation energy transfer from C706 to the C714 trap in the WT PSI and Red_b mutant is hampered as reflected by a weak emission at 712 nm. Large electron-phonon coupling strength (exposed via resonant hole-burned spectra) is consistent with a strong mixing of excited states with intermolecular charge transfer states leading to significantly red-shifted emission spectra. We conclude that excitation energy transfer in PSI is controlled by fine-tuning the electronic states of a small number of highly conserved red states. Finally, we show that mutations modify the protein potential energy landscape as revealed by different shapes and shifts of the blue- and red-shifted antiholes.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Frequency-Domain Spectroscopic Study of the Photosystem I Supercomplexes, Isolated IsiA Monomers, and the Intact IsiA Ring

The PSI 3 -IsiA 18 supercomplex is one of the largest and most complicated assemblies in photosynthesis. The IsiA ring, composed of 18 IsiA monomers (IsiA 18 ) surrounding the PSI trimer (PSI 3 ), forms under iron-deficient condition in cyanobacteria and acts as a peripheral antenna. Based on the supercomplex structure recently determined via cryo-EM imaging, we model various optical spectra of the IsiA monomers and IsiA 18 ring. Comparison of the absorption and emission spectra of the isolated IsiA monomers and the full ring reveals that about 2.7 chlorophylls (Chls) are lost in the isolated IsiA monomers. The best fits for isolated monomers spectra are obtained assuming the absence of Chl 508, Chl 517 and 70% loss of Chl 511. The best model describing all three hexamers and the entire ring suggests that the lowest energy pigments are Chls 511, 514 and 517. Based on the modeling results presented in this work we conclude that there are most likely three entry points for EET from the IsiA6 hexamer to the PSI core monomer, with two of these entry points likely being located next to each other (i.e. nine entry points from IsiA 18 to the PSI 3 trimer). Lastly, we show that excitation energy transfer inside individual monomers is fast (< 2 ps at T = 5 K) and at least 20 times faster than inter-monomer energy transfer.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Elucidating the Location of Cd 2+ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization 31 P and 113 Cd Solid-State NMR Spectroscopy

Indium phosphide quantum dots (InP QD) are a promising alternative to traditional QD materials that contain toxic heavy elements such as lead and cadmium. However, InP QD obtained from colloidal synthesis are often plagued by poor photoluminescence quantum yields (PL-QYs). In order to improve the PL-QY of InP QD, a number of post-synthetic treatments have been devised. Recently, it has been shown that InP post-synthetically treated with Lewis acid metal divalent cations (M-InP) exhibit enhanced PL-QY; however, the molecular structure and mechanism behind the improved PL-QY are not fully understood. Here, to determine the surface structure of M-InP QD, dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy (DNP SENS) experiments were employed on a series of InP magic size clusters treated with Cd ions, InP QD, cadmium phosphide (Cd 3 P 2 ) QD, and Cd-treated InP QD (Cd–InP QD). With the use of DNP SENS, we were able to obtain the 1D 31 P and 113 Cd NMR spectra, 113 Cd{ 31 P} rotational-echo double-resonance (REDOR) NMR spectra, and 31 P{ 113 Cd} dipolar heteronuclear multiple quantum correlation (D-HMQC) sequence. Changes in the phosphide 31 P chemical shifts after Cd treatment provide indirect evidence that some Cd alloys into the sub-surface regions of the particle. DNP-enhanced 113 Cd solid-state NMR spectra suggest that most Cd ions are coordinated by oxygen atoms from either carboxylate ligands or surface phosphate groups. 113 Cd{ 31 P} REDOR and 31 P{ 113 Cd} D-HMQC experiments confirm that a subset of Cd ions are located on the surface of Cd–InP QD and coordinated with phosphate groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Resonance Raman Study of Shell Morphology in InP/ZnSe/ZnS Core/Shell/Shell Nanocrystals

Resonance Raman spectra and absolute cross sections of InP/ZnSe/ZnS core/shell/shell nanocrystals have been obtained at excitation wavelengths of 501.7, 457.9, and 410 nm. Eight different structures having nearly the same lowest excitonic absorption wavelength but significantly different stoichiometries are compared. The Raman spectra show phonon features attributable to both the InP core and the ZnSe shell. The largest differences among the structures are seen in the ZnSe phonon region by using excitation at 457.9 nm, on the low-energy edge of the absorption features having significant contributions from the ZnSe shell. Here, structures that are nearly stoichiometric (In:P ratio ≈1.0) show a sharp, strongly polarized peak near the bulk ZnSe phonon frequency (~250 cm –1 ) and a weak lower-frequency shoulder with a higher depolarization ratio. Structures having excess indium show a stronger low-frequency shoulder near 225 cm –1 and lower integrated Raman intensities throughout the ZnSe phonon region. These changes are attributed to the presence of indium atoms in the ZnSe shell. Furthermore, these results support a previous assignment of a slow rise component in the time-resolved photoluminescence spectra of nonstoichiometric structures to transient trapping of holes at indium defects in the shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Charge ordering and structural transition in the new organic conductor {delta}'-(BEDT-TTF){sub 2}CF{sub 3}CF{sub 2}SO{sub 3}.

We report structural, transport, and optical properties and electronic structure calculations of the delta'-(BEDT-TTF) 2CF3CF2SO3 (BEDT-TTF = bis(ethylenedithio)-tetrathiafulvalene) organic conductor that has been synthesized by electrocrystallization. Electronic structure calculations demonstrate the quasi-one-dimensional Fermi surfaces of the compound, while the optical spectra are characteristic for a dimer-Mott insulator. The single-crystal X-ray diffraction measurements reveal the structural phase transition at 200 K from the ambient-temperature monoclinic P2(1)/m phase to the low-temperature orthorhombic Pca2(1) phase, while the resistivity measurements clearly show the first order semiconductor-semiconductor transition at the same temperature. This transition is accompanied by charge-ordering as it is confirmed by splitting of charge-sensitive vibrational modes observed in the Raman and infrared spectra. The horizontal stripe charge-order pattern is suggested based on the crystal structure, band structure calculations, and optical spectra.

Olejniczak, Iwona↗