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At least 451 records · Page 25

A Unifying View of Estimation and Control Using Belief Propagation With Application to Path Planning

The use of estimation techniques on stochastic models to solve control problems is an emerging paradigm that falls under the rubric of Active Inference (AI) and Control as Inference (CAI). In this work, we use probability propagation on factor graphs to show that various algorithms proposed in the literature can be seen as specific composition rules in a factor graph. We show how this unified approach, presented both in probability space and in log of the probability space, provides a very general framework that includes the Sum-product, the Max-product, Dynamic programming and mixed Reward/Entropy criteria-based algorithms. The framework also expands algorithmic design options that lead to new smoother or sharper policy distributions. We propose original recursions such as: a generalized Sum/Max-product algorithm, a Smooth Dynamic programming algorithm and a modified versions of the Reward/Entropy algorithm. The discussion is carried over with reference to a path planning problem where the recursions that arise from various cost functions, although they may appear similar in scope, bear noticeable differences. We provide a comprehensive table of composition rules and a comparison through simulations, first on a synthetic small grid with a single goal with obstacles, and then on a grid extrapolated from a real-world scene with multiple goals and a semantic map.

Francesco A. N. Palmieri↗

Finite-temperature many-body perturbation theory for anharmonic vibrations: Recursions, algebraic reduction, second-quantized reduction, diagrammatic rules, linked-diagram theorem, finite-temperature self-consistent field, and general-order algorithm

A unified theory is presented for finite-temperature many-body perturbation expansions of the anharmonic vibrational contributions to thermodynamic functions, i.e., the free energy, internal energy, and entropy. The theory is diagrammatically size-consistent at any order, as ensured by the linked-diagram theorem proved in this study, and, thus, applicable to molecular gases and solids on an equal footing. It is also a basis-set-free formalism, just like its underlying Bose–Einstein theory, capable of summing anharmonic effects over an infinite number of states analytically. It is formulated by the Rayleigh–Schrödinger-style recursions, generating sum-over-states formulas for the perturbation series, which unambiguously converges at the finite-temperature vibrational full-configuration-interaction limits. Two strategies are introduced to reduce these sum-over-states formulas into compact sum-over-modes analytical formulas. One is a purely algebraic method that factorizes each many-mode thermal average into a product of one-mode thermal averages, which are then evaluated by the thermal Born–Huang rules. Canonical forms of these rules are proposed, dramatically expediting the reduction process. The other is finite-temperature normal-ordered second quantization, which is fully developed in this study, including a proof of thermal Wick’s theorem and the derivation of a normal-ordered vibrational Hamiltonian at finite temperature. The latter naturally defines a finite-temperature extension of size-extensive vibrational self-consistent field theory. These reduced formulas can be represented graphically as Feynman diagrams with resolvent lines, which include anomalous and renormalization diagrams. Two order-by-order and one general-order algorithms of computing these perturbation corrections are implemented and applied up to the eighth order. The results show no signs of Kohn–Luttinger-type nonconvergence.

74 ATOMIC AND MOLECULAR PHYSICS↗

Sound generated in a cascade by three-dimensional disturbances convected in a subsonic flow

Discrete tone sound generation in a subsonic fan subject to three-dimensional disturbances is investigated. The analytical model used treats the fan rotor and stator as linear cascades of thin airfoils in a rectangular duct subject to a three-dimensional gust for which a complete aerodynamic theory already exists. The sound pressure can then be cast as the sum of a finite number of discrete sound waves (modes) the magnitude of which depends on an unknown function satisfying a singular integral equation. Similarity rules are derived to reduce the problem to that of a two-dimensional gust. Three-dimensional effects on the cut-off condition, the sound pressure, and the acoustic power are first investigated for each mode. The theory is then applied to noise generated by typical rotor-wake-defect and rotor-tip-vortex disturbances interacting with a stator.

Atassi, H.↗

Wormhole calculus, replicas, and entropies

We investigate contributions of spacetime wormholes, describing baby universe emission and absorption, to calculations of entropies and correlation functions, for example those based on the replica method. We find that the rules of the “wormhole calculus”, developed in the 1980s, together with standard quantum mechanical prescriptions for computing entropies and correlators, imply definite rules for limited patterns of connection between replica factors in simple calculations. These results stand in contrast with assumptions that all topologies connecting replicas should be summed over, and call into question the explanation for the latter. In a “free” approximation baby universes introduce probability distributions for coupling constants, and we review and extend arguments that successive experiments in a “parent” universe increasingly precisely fix such couplings, resulting in ultimately pure evolution. Once this has happened, the nontrivial question remains of how topology-changing effects can modify the standard description of black hole information loss.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Integral elastic, electronic-state, ionization, and total cross sections for electron scattering with furfural

We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20–250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section for electron–furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Masses of the PSR JO621+1002 Binary System Through Relativistic Apsidal Motion

Orbital, spin and astrometric parameters of the millisecond pulsar PSR J0621+1002 have been determined through six years of timing observations at three radio telescopes. The chief result is a measurement of the rate of periastron advance, omega=0 deg.0116 +/-0 deg.0008/yr. Interpreted as a general relativistic effect, this implies the sum of the pulsar mass, m(1), and the companion mass, m(2), to be M=m(1)+m(2)= 2.81 +/-0.30 solar mass. The Keplerian parameters rule out certain combinations of m(1) and m(2), as does the non-detection of Shapiro delay in the pulse arrival times. These constraints, together with the assumption that the companion is a white dwarf, lead to the maximum likelihood values m(1)=1.69((sup +0.30)(sub -0.30)) solar mass and m(2)=0.98((sup +0.32)(sub -0.12) solar mass (68% confidence). The other major finding is that the pulsar experiences dramatic variability in its dispersion measure (DM), with gradients as steep as 0.013 pc/cu cm/yr. A structure function analysis of the DM variations uncovers spatial fluctuations in the interstellar electron density that cannot be fit to a single power law, unlike the Kolmogorov turbulent spectrum that has been seen in the direction of other pulsars. Other results from the timing analysis include the first measurements of the pulsar's proper motion, mu=3.5+/-0.3 mas/yr, and of its spin-down rate, dP/dt=4.7 x 10(exp -20), which, when corrected for kinematic biases and combined with the pulse period, P=28.8 ms, gives a characteristic age of 1.1 x 10(exp 10) yr and a surface magnetic field strength of 1.2 x 10 (exp 9) G.

Spaver, Eric M.↗

Snowmass2021 CMB-HD White Paper

CMB-HD is a proposed millimeter-wave survey over half the sky that would be ultra-deep (0.5 uK-arcmin) and have unprecedented resolution (15 arcseconds at 150 GHz). Such a survey would answer many outstanding questions about the fundamental physics of the Universe. Major advances would be 1.) the use of gravitational lensing of the primordial microwave background to map the distribution of matter on small scales (k~10 h Mpc^(-1)), which probes dark matter particle properties. It will also allow 2.) measurements of the thermal and kinetic Sunyaev-Zel'dovich effects on small scales to map the gas density and velocity, another probe of cosmic structure. In addition, CMB-HD would allow us to cross critical thresholds: 3.) ruling out or detecting any new, light (< 0.1 eV) particles that were in thermal equilibrium with known particles in the early Universe, 4.) testing a wide class of multi-field models that could explain an epoch of inflation in the early Universe, and 5.) ruling out or detecting inflationary magnetic fields. CMB-HD would also provide world-leading constraints on 6.) axion-like particles, 7.) cosmic birefringence, 8.) the sum of the neutrino masses, and 9.) the dark energy equation of state. The CMB-HD survey would be delivered in 7.5 years of observing 20,000 square degrees of sky, using two new 30-meter-class off-axis crossed Dragone telescopes to be located at Cerro Toco in the Atacama Desert. Each telescope would field 800,000 detectors (200,000 pixels), for a total of 1.6 million detectors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Less-Complex Method of Classifying MPSK

An alternative to an optimal method of automated classification of signals modulated with M-ary phase-shift-keying (M-ary PSK or MPSK) has been derived. The alternative method is approximate, but it offers nearly optimal performance and entails much less complexity, which translates to much less computation time. Modulation classification is becoming increasingly important in radio-communication systems that utilize multiple data modulation schemes and include software-defined or software-controlled receivers. Such a receiver may "know" little a priori about an incoming signal but may be required to correctly classify its data rate, modulation type, and forward error-correction code before properly configuring itself to acquire and track the symbol timing, carrier frequency, and phase, and ultimately produce decoded bits. Modulation classification has long been an important component of military interception of initially unknown radio signals transmitted by adversaries. Modulation classification may also be useful for enabling cellular telephones to automatically recognize different signal types and configure themselves accordingly. The concept of modulation classification as outlined in the preceding paragraph is quite general. However, at the present early stage of development, and for the purpose of describing the present alternative method, the term "modulation classification" or simply "classification" signifies, more specifically, a distinction between M-ary and M'-ary PSK, where M and M' represent two different integer multiples of 2. Both the prior optimal method and the present alternative method require the acquisition of magnitude and phase values of a number (N) of consecutive baseband samples of the incoming signal + noise. The prior optimal method is based on a maximum- likelihood (ML) classification rule that requires a calculation of likelihood functions for the M and M' hypotheses: Each likelihood function is an integral, over a full cycle of carrier phase, of a complicated sum of functions of the baseband sample values, the carrier phase, the carrier-signal and noise magnitudes, and M or M'. Then the likelihood ratio, defined as the ratio between the likelihood functions, is computed, leading to the choice of whichever hypothesis - M or M'- is more likely. In the alternative method, the integral in each likelihood function is approximated by a sum over values of the integrand sampled at a number, 1, of equally spaced values of carrier phase. Used in this way, 1 is a parameter that can be adjusted to trade computational complexity against the probability of misclassification. In the limit as 1 approaches infinity, one obtains the integral form of the likelihood function and thus recovers the ML classification. The present approximate method has been tested in comparison with the ML method by means of computational simulations. The results of the simulations have shown that the performance (as quantified by probability of misclassification) of the approximate method is nearly indistinguishable from that of the ML method (see figure).

Hamkins, Jon↗

Supersonic and Moment-of-Area Rules Combined for Rapid Zero-Lift Wave-Drag Calculations

The concepts of the supersonic area rule and the moment-of-area rule are combined to develop a new method for calculating zero-lift wave drag which is amenable to the use of ordinary desk calculators. The total zero-lift wave drag of a configuration is calculated by the new method as the sum of the wave drag of each component alone plus the interference between components. In calculating the separate contributions each component or pair of components is analyzed over the smallest allowable length in order to improve the convergence of the series expression for the wave drag. The accuracy of the present method is evaluated by comparing the total zero-lift wave-drag solutions for several simplified configurations obtained by the present method with solutions given by slender-body and linearized theory. The accuracy and computational time required by the present method are also evaluated relative to the supersonic area rule and the moment-of-area rule. The results of the evaluation indicate that total zero-lift wave-drag solutions for simplified configurations can be obtained by the present method which differ from solutions given by slender-body and linearized theory by less than 6 percent. This accuracy for simplified configurations was obtained from only nine terms of the series expression for the wave drag as a result of calculating the total zero-lift wave drag by parts. For the same number of terms these results represent an accuracy greater than that for solutions obtained by either of the two methods upon which the present method is based, except in a few isolated cases. For the excepted cases, solutions by the present method and the supersonic area rule are identical. Solutions by the present method are obtained in one fifth the computing time required by the supersonic area rule. This difference in computing time of course would be substantially reduced if the complete procedures for both methods were programmed on electronic computing machines.

Levy, Lionel L., Jr.↗

SU-F-T-408: On the Determination of Equivalent Squares for Rectangular Small MV Photon Fields

Purpose: It is common practice to tabulate dosimetric data like output factors, scatter factors and detector signal correction factors for a set of square fields. In order to get the data for an arbitrary field, it is mapped to an equivalent square, having the same scatter as the field of interest. For rectangular fields both, tabulated data and empiric formula exist. We tested the applicability of such rules for very small fields. Methods: Using the Monte-Carlo method (EGSnrc-doseRZ), the dose to a point in 10cm depth in water was calculated for cylindrical impinging fluence distributions. Radii were from 0.5mm to 11.5mm with 1mm thickness of the rings. Different photon energies were investigated. With these data a matrix was constructed assigning the amount of dose to the field center to each matrix element. By summing up the elements belonging to a certain field, the dose for an arbitrary point in 10cm depth could be determined. This was done for rectangles up to 21mm side length. Comparing the dose to square field results, equivalent squares could be assigned. The results were compared to using the geometrical mean and the 4Xperimeter/area rule. Results: For side length differences less than 2mm, the difference between all methods was in general less than 0.2mm. For more elongated fields, relevant differences of more than 1mm and up to 3mm for the fields investigated occurred. The mean square side length calculated from both empiric formulas fitted much better, deviating hardly more than 1mm and for the very elongated fields only. Conclusion: For small rectangular photon fields, deviating only moderately from square both investigated empiric methods are sufficiently accurate. As the deviations often differ regarding their sign, using the mean improves the accuracy and the useable elongation range. For ratios larger than 2, Monte-Carlo generated data are recommended. SW is funded by Deutsche Forschungsgemeinschaft (SA481/10-1)

60 APPLIED LIFE SCIENCES↗

Mechanical Testing of MLCCs

Cracking of multilayer ceramic capacitors, MLCCs, remains a serious problem for space systems. This problem increases substantially for large size capacitors and in cases when manual soldering is involved or the system experiences mechanical shock or vibration. In any case, a fracture occurs when the sum of external and internal mechanical stresses exceeds the strength of the part. To reduce the probability of cracking, the level of stress should be reduced, e.g. by optimizing the assembly workmanship and rules for board design, and the strength of the parts increased by selecting the most mechanically robust capacitors. The latter might possibly be achieved by selecting MLCCs based on the in-situ measurements of mechanical characteristics using four types of tests: flexural strength, hardness, fracture toughness, and flex bend testing. Note that military specifications MIL-PRF-123 and MIL-PRF-55681 do not have requirements for mechanical testing of the parts. However, specifications for automotive industry components employ two types of mechanical tests: beam load (break strength) test per AEC-Q200-003 and board flex test per AEC-Q200-005. A recent military specification for thin dielectric capacitors, MIL-PRF-32535, has one mechanical test, board flex testing, that is similar to AEC-Q200-005. The purpose of this report was assessment of the efficiency of different mechanical tests for selection robust capacitors and comparison of mechanical characteristics of Base Metal Electrode (BME) and Precious Metal Electrode (PME) capacitors. The report has three parts related to the first three mechanical tests mentioned above.

Precious Metal Electrode (PME) capacitors↗

Lessons from the Ramond sector

We revisit the consistency of torus partition functions in (1+1)d fermionic conformal field theories, combining old ingredients of modular invariance/covariance with a modernized understanding of bosonization/fermionization dualities. Various lessons can be learned by simply examining the oft-ignored Ramond sector. For several extremal/kinky modular functions in the bootstrap literature, we can either rule out or identify the underlying theory. We also revisit the N = 1 Maloney-Witten partition function by calculating the spectrum in the Ramond sector, and further extending it to include the modular sum of seed Ramond characters. Finally, we perform the full N = 1 RNS modular bootstrap and obtain new universal results on the existence of relevant deformations preserving different amounts of supersymmetry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The renormalization scale-setting problem in QCD

A key problem in making precise perturbative QCD predictions is to set the proper renormalization scale of the running coupling. The conventional scale-setting procedure assigns an arbitrary range and an arbitrary systematic error to fixed-order pQCD predictions. In fact, this ad hoc procedure gives results which depend on the choice of the renormalization scheme, and it is in conflict with the standard scale-setting procedure used in QED. Predictions for physical results should be independent of the choice of the scheme or other theoretical conventions. We review current ideas and points of view on how to deal with the renormalization scale ambiguity and show how to obtain renormalization scheme- and scale-independent estimates. We begin by introducing the renormalization group (RG) equation and an extended version, which expresses the invariance of physical observables under both the renormalization scheme and scale-parameter transformations. The RG equation provides a convenient way for estimating the scheme- and scale-dependence of a physical process. We then discuss self-consistency requirements of the RG equations, such as reflexivity, symmetry, and transitivity, which must be satisfied by a scale-setting method. Four typical scale setting methods suggested in the literature, i.e., the Fastest Apparent Convergence (FAC) criterion, the Principle of Minimum Sensitivity (PMS), the Brodsky–Lepage–Mackenzie method (BLM), and the Principle of Maximum Conformality (PMC), are introduced. Basic properties and their applications are discussed. We pay particular attention to the PMC, which satisfies all of the requirements of RG invariance. Using the PMC, all non-conformal terms associated with the β-function in the perturbative series are summed into the running coupling, and one obtains a unique, scale-fixed, scheme-independent prediction at any finite order. The PMC provides the principle underlying the BLM method, since it gives the general rule for extending BLM up to any perturbative order; in fact, they are equivalent to each other through the PMC–BLM correspondence principle. Thus, all the features previously observed in the BLM literature are also adaptable to the PMC. The PMC scales and the resulting finite-order PMC predictions are to high accuracy independent of the choice of the initial renormalization scale, and thus consistent with RG invariance. The PMC is also consistent with the renormalization scale-setting procedure for QED in the zero-color limit. The use of the PMC thus eliminates a serious systematic scale error in perturbative QCD predictions, greatly improving the precision of empirical tests of the Standard Model and their sensitivity to new physics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A phase-field fracture formulation for generalized standard materials: The interplay between thermomechanics and damage

Accurately modeling fracture of ductile materials poses open challenges in the field of computational mechanics due to the multiphysics nature of their failure processes. Integrating the interplay between thermodynamics and damage into ductile fracture models is vital for predicting critical failure modes. Here, in this paper, we develop a versatile phase-field (PF) framework for modeling ductile fracture, taking into account finite-strain elasto-plasticity. The framework stems from a variational formulation of constitutive relations for generalized standard materials (GSMs), whose response is described by a Helmholtz free energy and a dissipation pseudo-potential. Its variational structure is based on a minimum principle for a functional that expresses the sum of power densities for reversible and irreversible processes. By minimizing this functional with a constraint on a von Mises yield function, we derive the evolution equation for the equivalent plastic strain and an associative flow rule. This constrained optimization problem is analytically solved for a wide class of thermo-viscoplasticity models. The key innovations of the current work include (i) a cubic plastic degradation function that accounts for a non-vanishing damage-dependent yield stress, (ii) closed-form expressions of the Helmholtz free energy and dissipation pseudo-potential for three thermo-viscoplasticity models, (iii) an extended Johnson–Cook plasticity model with a nonlinear hardening law, and (iv) a plastic work heat source that depends on the plastic degradation function and a variable Taylor–Quinney (TQ) coefficient. The capabilities of the proposed framework are tested with the aid of four ductile fracture problems, including the Sandia Fracture Challenge. In each of these problems, we examine the evolution of relevant field variables such as the PF order parameter, the equivalent plastic strain, the temperature, and the internal power dissipation density, in addition to the overall structural response quantified by the force–displacement curve. These numerical studies demonstrate that the proposed framework effectively represents ductile fracture, yielding computational results that exhibit good agreement with experimental data.

36 MATERIALS SCIENCE↗

Nonlinear X-ray Optics

Novel X-ray free-electron lasers (XFELs) are capable of producing radiation with unprecedented properties. Specifically, their ultrashort coherent X-ray pulses can generate extreme peak intensities where ordinary rules of light-matter interaction may no longer apply, and nonlinear processes start to become important. XFELs have made it possible to observe some of the most important coherent non-sequential nonlinearities, including X-ray-optical sum frequency generation (SFG), X-ray second harmonic generation (XSHG), two-photon absorption (TPA) and nonlinear two-photon Compton scattering (2PCS). In particular, the 2PCS experiment has led to unexpected results, namely the observation of a substantial anomalous red shift in the energy of photons generated by nonlinear two-photon X-ray Compton scattering in beryllium. The energy shift is in addition to the predicted nonlinear Compton shift and was neither expected from extrapolations from linear X-ray interactions nor from nonlinear effects at optical wavelengths. Our results suggest a novel nonlinear scattering mechanism that can only be observed at high fields at X-ray wavelengths, where the photon energy is a significant fraction of the electron rest mass (and thus a significant momentum transfer to the electron occurs during the scattering) and where the interaction is not dominated by the quiver motion of the electron in the field (ponderomotive potential) as is usually the case at longer (optical) wavelengths. The goal of this research project was the investigation of fundamental nonlinear X-ray-matter interactions. As these processes are typically weak, part of this research is the exploration of more efficient nonlinear X-ray processes by studying novel mechanisms including solid-state effects, the assistance of optical radiation and novel phase-matching techniques. These experiments require extremely large X-ray field strengths, such as produced by XFELs. Nonlinear X-ray effects can lead to important applications in many research fields. For example, it could lead to instantaneous plasma diagnostics for materials in extreme conditions, as a method for combining atomic-scale structural sensitivity with chemical specificity, or as a probe of electron dynamics in solids on the attosecond (1 as = 10 -18 s) time- and Ångstrom (10 -10 m) length scales. In addition, a detailed understanding of nonlinear X-ray matter interactions is crucial for understanding and extending the limits of structural determination at high intensity such as in serial femto-crystallography. The results could have a profound impact on advanced XFEL light sources such as the LCLS-II.

47 OTHER INSTRUMENTATION↗

A comparison of methods for DPLL loop filter design

Four design methodologies for loop filters for a class of digital phase-locked loops (DPLLs) are presented. The first design maps an optimum analog filter into the digital domain; the second approach designs a filter that minimizes in discrete time weighted combination of the variance of the phase error due to noise and the sum square of the deterministic phase error component; the third method uses Kalman filter estimation theory to design a filter composed of a least squares fading memory estimator and a predictor. The last design relies on classical theory, including rules for the design of compensators. Linear analysis is used throughout the article to compare different designs, and includes stability, steady state performance and transient behavior of the loops. Design methodology is not critical when the loop update rate can be made high relative to loop bandwidth, as the performance approaches that of continuous time. For low update rates, however, the miminization method is significantly superior to the other methods.

Aguirre, S.↗

Time-dependent approach to spin-vibronic coupling: Implementation and assessment

In this work, we present the generalization of a time-dependent method for the calculation of intersystem crossing (ISC) rates in the Condon approximation. When ISC takes place between electronic states with the same orbital type, i.e., when the transition is forbidden according to the El-Sayed rules, it is necessary to go beyond the Condon approximation. Similar to the Herzberg-Teller expansion of the vibronic interaction, the electronic spin–orbit matrix elements are assumed to depend linearly on the nuclear coordinates. The ISC rate is then a sum of three contributions: a direct, mixed direct-vibronic, and vibronic term. The method, presented in this work, is based on the generating function formalism and the multi-mode harmonic oscillator approximation. In addition to the zero-temperature case, we implemented formulae for finite-temperature conditions assuming a Boltzmann population of vibrational levels in the initial state. Tests have been carried out for a variety of molecules for which literature data were available. We computed vibronic one-photon spectra of free-base porphyrin and free-base chlorin and calculated ISC rates for xanthone, thioxanthone, thionine, as well as free-base porphyrin and found excellent agreement with previous results. Quantitative rates for triplet formation in rhodamine A have been determined theoretically for the first time. We find the S{sub 1}↝ T{sub 2} channel to be the major source of triplet rhodamine formation in the gas phase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electronic excitations of α - Fe 2 O 3 heteroepitaxial films measured by resonant inelastic x-ray scattering at the Fe L edge

Resonant inelastic x-ray scattering (RIXS) spectra of hematite (α-Fe 2 O 3 ) were measured at the Fe L 3 edge for heteroepitaxial thin films which were undoped and doped with 1% Ti, Sn, or Zn, in the energy-loss range in excess of 1 eV to study electronic transitions. The spectra were measured for several momentum transfers q, conducted at both low temperature (T=14 K) and room temperature. While we cannot rule out dispersive features possibly owing to propagating excitations, the coarse envelopes of the general spectra did not appreciably change shape with q, implying that the bulk of the observed L-edge RIXS intensity originates from (mostly) nondispersive ligand field excitations. Summing the RIXS spectra over q and comparing the results at T=14 K to those at T=300 K revealed pronounced temperature effects, including an intensity change and energy shift of the ≈1.4 eV peak, a broadband intensity increase of the 3-4 eV range, and higher energy features. The q-summed spectra and their temperature dependencies are virtually identical for nearly all of the samples with different dopants, save for the temperature dependence of the Ti-doped sample's spectrum, which we attribute to being affected by a large number of free charge carriers. Comparing with magnetization measurements for different temperatures and dopings likewise did not show a clear correlation between the RIXS spectra and the magnetic ordering states. To clarify the excited states, we performed spin multiplet calculations which were in excellent agreement with the RIXS spectra over a wide energy range and provide detailed electronic descriptions of the excited states. Furthermore, the implications of these findings to the photoconversion efficiency of hematite photoanodes is discussed.

36 MATERIALS SCIENCE↗