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Optical nonlinear spectroscopies carry a high amount of information about the systems under investigation; however, as they report polarization signals, the resulting spectra are often congested and difficult to interpret. To recover the landscape of energy states and physical processes such as energy and electron transfer, a clear interpretation of the nonlinear signals is prerequisite. Here, we focus on the interpretation of the electrochromic band-shift signal, which is generated when an internal electric field is established in the system following optical excitation. Whereas the derivative shape of the band-shift signal is well understood in transient absorption spectroscopy, its emergence in two-dimensional electronic spectroscopy (2DES) has not been discussed. In this work, we employed 2DES to follow the dynamic band-shift signal in reaction centers of purple bacteria Rhodobacter sphaeroides at 77 K. The prominent two-dimensional derivative-shape signal appears with the characteristic formation time of the charge separated state. To explain and characterize the band-shift signal, we use expanded double-sided Feynman diagram formalism. We propose to distinguish two types of Feynman diagrams that lead to signals with negative amplitude: excited state absorption and re-excitation. The presented signal decomposition and modeling analysis allows us to recover precise electrochromic shifts of accessory bacteriochlorophylls, identify additional signals in the B band range, and gain a further insight into the electron transfer mechanism. In a broader perspective, expanded Feynman diagram formalism will allow for interpretation of all 2D signals in a clearer and more intuitive way and therefore facilitate studying the underlying photophysics.

Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Förster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a purely electronic excitonic coupling model. Energy transfer can leave excess energy behind as vibration on the electronic ground state of the donor, allowing vibrational relaxation on the donor's ground electronic state to make energy transfer permanent by removing excess energy from the excited electronic state of the dimer.

Excitation energy transfer in complex systems often proceeds through series of intermediate states. One of the goals of time-resolved spectroscopy is to identify the spectral signatures of all of them in the acquired experimental data and to characterize the energy transfer scheme between them. It is well known that in the case of transient absorption spectra such decomposition is ambiguous even if many simplifying considerations are taken. In contrast to transient absorption, absorptive 2D spectra intuitively resemble population transfer matrices. Therefore, it seems possible to decompose the 2D spectra unambiguously. Here we show that all necessary information is encoded in the combination of absorptive 2D and linear absorption spectra. We set up a simple model describing a broad class of absorptive 2D spectra and prove analytically that they can be inverted uniquely towards physical parameters fully determining the species-associated spectra of individual constituents together with all connecting intrinsic rate constants. Due to the matrix formulation of the model, it is suitable for fast computer calculation necessary to efficiently perform the inversion numerically by fitting the combination of experimental 2D and absorption spectra. Moreover, the model allows for decomposition of the 2D spectrum into its stimulated emission, ground-state bleach, and excited-state absorption components almost unambiguously. The numerical procedure is illustrated exemplarily.

Several recent experiments report on possibility of dark-state detection by means of so called beating maps of two-dimensional photon-echo spectroscopy [Ostroumov et al., Science 340, 52 (2013); Bakulin et al., Ultrafast Phenomena XIX (Springer International Publishing, 2015)]. The main idea of this detection scheme is to use coherence induced upon the laser excitation as a very sensitive probe. In this study, we investigate the performance of ground-state coherence in the detection of dark electronic states. For this purpose, we simulate beating maps of several models where the excited-state coherence can be hardly detected and is assumed not to contribute to the beating maps. The models represent strongly coupled electron-nuclear dynamics involving avoided crossings and conical intersections. In all the models, the initially populated optically accessible excited state decays to a lower-lying dark state within few hundreds femtoseconds. We address the role of Raman modes and of interstate-coupling nature. Our findings suggest that the presence of low-frequency Raman active modes significantly increases the chances for detection of dark states populated via avoided crossings, whereas conical intersections represent a more challenging task.

We report differential cross sections (DCSs) for electron-impact vibrational-excitation of tetrahydrofuran, at intermediate incident electron energies (15-50 eV) and over the 10°-90° scattered electron angular range. These measurements extend the available DCS data for vibrational excitation for this species, which have previously been obtained at lower incident electron energies (≤20 eV). Where possible, our data are compared to the earlier measurements in the overlapping energy ranges. Here, quite good agreement was generally observed where the measurements overlapped.

In this paper, we report newly derived integral cross sections (ICSs) for electron impact vibrational excitation of tetrahydrofuran (THF) at intermediate impact energies. These cross sections extend the currently available data from 20 to 50 eV. Further, they indicate that the previously recommended THF ICS set [Garland et al., Phys. Rev. A 88, 062712 (2013)] underestimated the strength of the electron-impact vibrational excitation processes. Thus, that recommended vibrational cross section set is revised to address those deficiencies. Electron swarm transport properties were calculated with the amended vibrational cross section set, to quantify the role of electron-driven vibrational excitation in describing the macroscopic swarm phenomena. Here, significant differences of up to 17% in the transport coefficients were observed between the calculations performed using the original and revised cross section sets for vibrational excitation.

The Fenna-Matthews-Olson (FMO) protein-pigment complex acts as a molecular wire conducting energy between the outer antenna system and the reaction center; it is an important photosynthetic system to study the transfer of excitonic energy. Recent crystallographic studies report the existence of an additional (eighth) bacteriochlorophyll a (BChl a) in some of the FMO monomers. To understand the functionality of this eighth BChl, we simulated the two-dimensional electronic spectra of both the 7-site (apo form) and the 8-site (holo form) variant of the FMO complex from green sulfur bacteria, Prosthecochloris aestuarii. By comparing the spectrum, it was found that the eighth BChl can affect two different excitonic energy transfer pathways: (1) it is directly involved in the first apo form pathway (6 → 3 → 1) by passing the excitonic energy to exciton 6; and (2) it facilitates an increase in the excitonic wave function overlap between excitons 4 and 5 in the second pathway (7 → 4,5 → 2 → 1) and thus increases the possible downward sampling routes across the BChls.

2,4,6-trichloroanisole and 2,4,6-tribromoanisole were investigated by means of electron transmission spectroscopy and two different types of dissociative electron attachment spectrometers. The results obtained were interpreted with the support of density functional theory calculations. The dominant dissociative decay channels of the temporary molecular negative ions lead to the formation of Cl- and Br-in the low electron energy region. Formation of long-lived parent anions is observed at thermal electron energies. Their relative intensity depends on the experimental time window, ∼36 μs in the case of the static magnet mass analyzer and ∼200 μs for the quadrupole mass analyzer employed. The results obtained may be useful for rapid detection of these compounds in wine and pharmaceutical industries, as well as other branches connected to the food industry, e.g., packaging. [ABSTRACT FROM AUTHOR]

Herein, terahertz (THz) time domain spectroscopy is used to measure the complex conductivity of semi-insulating CoFe2O4 nanoparticles (NPs) and nano-hollow spheres (NHSs) with different diameters ranging from 100 to 350 nm having a nanocrystalline shell thickness of 19 to 90 nm, respectively. Interestingly, the magnitude of conductivity for CoFe2O4 NPs and NHSs of same average diameter (∼100 nm) for a given frequency of 0.3 THz is found to be 0.33 S/m and 9.08 S/m, respectively, indicating that the hollow structure exhibits greater THz conduction in comparison to its solid counterpart. Moreover, THz conductivity can be tailored by varying the nano-shell thickness of NHSs, and a maximum conductivity of 15.61 S/m is observed at 0.3 THz for NHSs of average diameter 250 nm. A detailed study reveals that thermally activated polaronic hopping plays the key role in determining the electrical transport property of CoFe2O4 nanostructures, which is found to solely depend on their magnitude of THz absorptivity. The non-Drude conductivity of all CoFe2O4 nanostructures is well described by the Polaron model instead of the Drude-Smith model, which is relevant for backscattering of free electrons in a nanostructured material. The Polaron model includes intra-particle and interparticle polaronic conductivities for closely spaced magnetic nanostructures and provides a mean free path of 29nm for CoFe2O4 NPs of diameter 100nm, which is comparable with its average crystallite size, indicating the applicability of the developed model for nanomaterials where charge transport is determined by polaronic hopping. Finally, we have demonstrated the morphology and size dependent magnetic measurements of ferrimagnetically aligned CoFe2O4 nanostructures through a vibrating sample magnetometer in the temperature range of 80-250 K, revealing that the disordered surface spin layer of nanostructures significantly controls their magnetism. [ABSTRACT FROM AUTHOR]

The electron g factor in an ensemble of InAs/InP quantum dots with emission wavelengths around 1.4 μm is measured using time-resolved pump-probe Faraday rotation spectroscopy in different magnetic field orientations. Thereby, we can extend recent single dot photoluminescence measurements significantly towards lower optical transition energies through 0.86 eV. This allows us to obtain detailed insight into the dispersion of the recently discovered g factor anisotropy in these infrared emitting quantum dots. We find with decreasing transition energy over a range of 50 meV a strong enhancement of the g factor difference between magnetic field normal and along the dot growth axis, namely, from 1 to 1.7. We argue that the g factor cannot be solely determined by the confinement energy, but the dot asymmetry underlying this anisotropy therefore has to increase with increasing dot size. [ABSTRACT FROM AUTHOR]

Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2. [ABSTRACT FROM AUTHOR]

The temperature dependence of the electron Landé g-factor in bulk cubic GaN is investigated over an extremely broad temperature range from 15K up to 500K by time-resolved Kerr-rotation spectroscopy. The g-factor is found to be approximately constant over the full investigated temperature range. Calculations by k · p-theory predict a negligible temperature dependence g(T) in complete agreement with the experiment as a consequence of the large band-gap and small spin orbit splitting in cubic GaN. [ABSTRACT FROM AUTHOR]

The effect of hole transport on the performance of infrared light emitting diodes (LED) was investigated. The active area of the LEDs comprised two type-II superlattices with different periods and widths connected in series. Electroluminescence spectra of the devices with different positions of long wave and mid wave superlattice sections were mostly contributed by the superlattice closest to the p-contact. The experimental results indicate that due to suppressed vertical hole transport, the recombination of electrically injected electrons and holes in a type II superlattice LED active region takes place within a few superlattice periods near p-barrier. Possible reason for the effect is reduction of hole diffusion coefficient in an active area of a superlattice LED under bias. [ABSTRACT FROM AUTHOR]

Two-dimensional electronic spectroscopy (2DES) is a powerful method to probe the coherent electron dynamics in complicated systems. Stabilizing the phase difference of the incident ultrashort pulses is the most challenging part for experimental demonstration of 2DES. Here, we present a tutorial review on the 2DES protocols based on active phase managements which are originally developed for quantum optics experiments. We introduce the 2DES techniques in box and pump-probe geometries with phase stabilization realized by interferometry, and outline the fully collinear 2DES approach with the frequency tagging by acoustic optical modulators and frequency combs. The combination of active phase managements, ultrashort pulses and other spectroscopic methods may open new opportunities to tackle essential challenges related to excited states. [ABSTRACT FROM AUTHOR]

We report the electrical properties of 60° dislocations originating from the +1.2% lattice mismatch between an unintentionally doped, 315 nm thick Ge0.922Sn0.078 layer (58% relaxed) and the underlying Ge substrate, using deep level transient spectroscopy. The 60° dislocations are found to be split into Shockley partials, binding a stacking fault. The dislocations exhibit a band-like distribution of electronic states in the bandgap, with the highest occupied defect state at ∼EV + 0.15 eV, indicating no interaction with point defects in the dislocation's strain field. A small capture cross-section of 1.5 × 10−19 cm2 with a capture barrier of 60 meV is observed, indicating a donor-like nature of the defect-states. Thus, these dislocation-states are not the source of unintentional p-type doping in the Ge0.922Sn0.078 layer. Importantly, we show that the resolved 60° dislocation-states act as a source of leakage current by thermally generating minority electrons via the Shockley-Read-Hall mechanism. [ABSTRACT FROM AUTHOR]

The distribution of photoelectrons acquired in angle-resolved photoemission spectroscopy can be mapped onto the energy-momentum space of the Bloch electrons in the crystal. The explicit forms of the mapping function f depend on the configuration of the apparatus as well as on the type of the photoelectron analyzer. We show that the existence of the analytic forms of f−1 is guaranteed in a variety of setups. The variety includes the case when the analyzer is equipped with a photoelectron deflector. Thereby, we provide a demonstrative mapping program implemented by an algorithm that utilizes both f and f−1. The mapping methodology is also usable in other spectroscopic methods such as momentum-resolved electron-energy loss spectroscopy. [ABSTRACT FROM AUTHOR]

Tungsten diselenide (WSe2) was analyzed using x-ray photoelectron spectroscopy. A freshly exfoliated, oxygen-free flake was analyzed. Spectral regions for O 1s, W 4d, W 4f, W 5p, Se 3d and an extended region encompassing Se 3p, Se 3s, W 4d, Se LMM, and C 1s were acquired along with the valence band. Bulk quantitative analyses by x-ray fluorescence and x-ray diffraction indicated the material was stoichiometric and phase pure, respectively. [ABSTRACT FROM AUTHOR]

The problem of the electron spectrum in a quasi-two-dimensional space (such as interfaces, heterostructures, and surfaces) is set up and analytically solved based on the fundamental Dirac equation. It is demonstrated that using the unitary transformation method and the method of spin invariants to solve the Dirac equation leads to identical results. The eigen bispinors of the Dirac equation are found, and the way in which their diversity arises due to the arbitrariness of the spin-quantization axis direction is demonstrated. The features of electron behavior in a parabolic quantum well are considered. [ABSTRACT FROM AUTHOR]

Doppler-free saturation spectroscopy provides a very powerful method to obtain detailed information about the electronic structure of the atom through measurement of the spectral line profile. This is achieved through a significant decrease in the Doppler broadening and essentially an elimination of the instrument broadening inherent to passive spectroscopic techniques. In this paper we present the technique and associated physics of Doppler-free saturation spectroscopy in addition to how one selects the appropriate transition. Simulations of Hδ spectra are presented to illustrate the increased sensitivity to both electric field and electron density measurements. [ABSTRACT FROM AUTHOR]

Recently, the general electromagnetic fluctuation theory for magnetized plasmas has been used to study the steady-state fluctuation spectra and the total intensity of low-frequency collective weakly damped modes for parallel wave vectors in Maxwellian plasmas. Now, we address the same question with respect to an arbitrary direction of the wave-vector. Here, we analyze this problem for equal mass plasmas. These plasmas are a very good tool to study various plasma phenomena, as they considerably facilitate the theoretical consideration and at the same time provide with their clear physical picture. Finally, we compare our results in the limiting case of parallel wave vectors with the previous study. [ABSTRACT FROM AUTHOR]

We report on intraband photocurrent spectroscopy of dome-shaped GeSi islands embedded in a Si matrix with n+-type bottom and top Si layers. An in-plane polarized photoresponse in the 85-160 meV energy region has been observed and ascribed to the optical excitation of electrons from states confined in the strained Si near the dome apexes to the continuum states of unstrained Si. The electron confinement is caused by a modification of the conduction band alignment induced by inhomogeneous tensile strain in Si around the buried GeSi quantum dots. Sensitivity of the device to the normal incidence radiation proves a zero-dimensional nature of confined electronic wave functions. [ABSTRACT FROM AUTHOR]