Resonance Raman scattering in graphene: Probing phonons and electrons

In this work, by using different laser excitation energies, we obtain important electronic and vibrational properties of mono- and bi-layer graphene. For monolayer graphene, we determine the phonon dispersion near the Dirac point for the in-plane transverse optical (iTO) mode. This result is compared with recent calculations that take into account electron–electron correlations for the phonon dispersion around the K point. For bilayer graphene we extract the Slonczewski–Weiss–McClure band parameters and compare them with recent infrared measurements. We also analyze the second-order feature in the Raman spectrum for trilayer graphene.     

Raman spectroscopy study of twisted tetralayer graphene

We present a systematic Raman study of twisted tetralayer graphene (t(2 + 2)LG), under excitation of two laser lines. In t(2 + 2)LG samples, top Bernal stacked bilayer graphene (2LG stands for Bernal‐stacked bilayer graphene) twists different angle relative to bottom 2LG. It is found that 2D and 2D′ peaks of t(2 + 2)LG show positive wavenumber shift relative to those of 2LG. We propose a simplified electronic band structure for t(2 + 2)LG; interlayer interaction‐induced changing in electronic band structure can be used to understand the aforementioned spectral features. The electronic structures of t(2 + 2)LG samples are then probed from resonant Raman studies of 2D and 2D′ peaks using two laser lines; electronic dispersions in t(2 + 2)LG samples are given. Our study facilitates understanding of twist angle‐dependent electronic properties of tetralayer graphene superlattice. Copyright © 2016 John Wiley & Sons, Ltd.     

Excitonic effects of bilayer graphene: A simple approach

The present work investigates the excitonic effects on the bilayer graphene with layers of different thickness under the influence of external electric field through a simple numerical approach. The band structure and energy gap have been calculated using a tight-binding model including parameters like the second-nearest-neighbor-hopping energies t′ (in-plane) and γ (intra-layer) and the on-site energy Δ, in details. The binding energy of exciton for bilayer graphene has been calculated by Wannier model and Hartree–Fock approximation through the Bethe–Salpeter equation. Finally the optical conductivity spectrum of bilayer graphene has been calculated by using the effective mass approximation in two band model.     

用受激拉曼泵浦方法高效制备v=2振动激发态氘分子

We report the preparation of D₂ molecules in v=2 level in molecular beam condition. A single longitudinal mode laser system was used for excitation of D₂ from (v=0, j=0) to (v=2, j=0) with the scheme of stimulated Raman pumping. An excitation efficiency of 25.2% has been achieved, which was determined by the scheme of resonance-enhanced multiphoton ionization. Dependence of relative excitation efficiency on laser energy has been measured. We found that the increasing rate of excitation efficiency became slower as pulse energy of Stokes laser increase, while the excitation efficiency still increases approximately linearly with pump pulse energies up to 60 mJ. The spectral line shapes of Raman transition was also measured at different laser energies and considerable dynamical Stark effect was observed. A single peak was found on the three dimension surface of relative excitation efficiency, indicating the process occurred in the present study is a process of stimulated Raman pumping instead of stimulated adiabatic Raman passage.     

Raman Excitation Profile of the G-band Enhancement in Twisted Bilayer Graphene

A resonant Raman study of twisted bilayer graphene (TBG) samples with different twisting angles using many different laser lines in the visible range is presented. The samples were fabricated by CVD technique and transferred to Si/SiO₂ substrates. The Raman excitation profiles of the huge enhancement of the G-band intensity for a group of different TBG flakes were obtained experimentally, and the analysis of the profiles using a theoretical expression for the Raman intensities allowed us to obtain the energies of the van Hove singularities generated by the Moiré patterns and the lifetimes of the excited state of the Raman process. Our results exhibit a good agreement between experimental and calculated energies for van Hove singularities and show that the lifetime of photoexcited carrier does not depend significantly on the twisting angle in the range intermediate angles (?? between 10^° and 15^°). We observed that the width of the resonance window (Γ ≈ 250 meV) is much larger than the REP of the Raman modes of carbon nanotubes, which are also enhanced by resonances with van Hove singularities.     

Raman spectrum of vanadium pentoxide from density‐functional perturbation theory

We present ab initio calculation within the framework of the density‐functional theory (DFT) on band structure and vibrational properties of bulk V₂O₅. The structure of V₂O₅ comes from optimization of the experimental data with lattice parameters fixed. The band structure of the optimized structure has been calculated, and the result fits the experimental data very well and also gives similar results as those calculated by other methods. The phonon eigenwavenumbers of the Γ‐ point of V₂O₅ bulk have been calculated ab initio in density‐functional perturbation theory (DFPT). The calculated vibrational wavenumbers are in good agreement with observed infrared and Raman wavenumbers, and the predictive full phonon dispersion of bulk V₂O₅ has also been obtained. Further we calculated the Raman spectrum of vanadium pentoxide (V₂O₅) powder sample using the obtained Raman susceptibility. Calculated and measured intensities show overall good agreement. Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical rovibrational spectroscopy beyond fc-CCSD(T): the cation CNC+

An accurate near-equilibrium potential energy surface (PES) for CNC⁺ is constructed based on a high-level composite ab initio method. By combining explicitly correlated all-electron CCSD(T)-F12b with scalar relativistic effects and higher order correlation up to coupled cluster theory with singles, doubles, triples and quadruples (CCSDTQ) we achieve convergence in the wavenumbers of the fundamentals to ca. 1 cm^?1. Rovibrational energies are calculated in a variational approach and vibrational term energies and rotational constants are in excellent agreement with available experimental data. Accurate values for centrifugal distortion constants of CNC⁺ in different vibrational states are predicted. Especially the centrifugal distortion constants in the vibrational ground state of D₀ = 0.563 · 10^?6 cm^?1 and H₀ = 0.188 · 10^?10 cm^?1 should be superior to experimentally derived values. Reassignments of some experimentally observed transitions are suggested based on a comparison of experimental and calculated term differences. The bending part of the PES appears to be almost quartic and the band origin of the bending vibration is predicted at 94.2 cm^?1. Absolute line intensities are calculated for various transitions in CNC⁺. For the bending vibration, an intensity is predicted that is three orders of magnitude smaller than for the antisymmetric stretching vibration.     

Quasiholes in a MgZnO/ZnO Heterojunction as Vacancions

Recombination of two-dimensional electrons of a low density in a MgZnO/ZnO heterojunction with localized valence-band holes is considered. It is suggested that quasiholes appearing in the process of photoluminescence of strongly interacting two-dimensional electrons should be considered as vacancion quasiparticles in a quantum Wigner crystal. Vacancions formed upon the removal of an electron from the crystal are delocalized owing to the tunneling effect. The vacancion energies E(k) form a band of width D that depends on the probability of vacancy tunneling. The width D corresponds to the width of the photoluminescence band of the two-dimensional electron system. The shape of the photoluminescence band of the Wigner crystal is obtained using the tight-binding approximation for the vacancion dispersion relation E(k) is compared with experimental results.

     

Infrared absorption spectra of few-layer graphenes studied by first principles calculations

The infrared (IR) absorption spectra of the undoped, the hole- and electron-doped few-layer graphene (FLG) with layer number of N=1,2,3 have been calculated using the density functional theory in the local density approximation. It is found that in contrast with the featureless optical spectrum of the undoped monolayer graphene, the undoped AB-stacking bilayer and trilayer graphenes exhibit interesting rich IR spectra, e.g., the peaks and jumps in their IR spectra, which are caused by the coupling between different layers. And clear characteristic peaks, lying at different energies, exist in the IR spectra of the hole- or electron-doped bilayer and trilayer graphenes due to the asymmetrical band structures. Beside, based upon their different IR spectra, a powerful experimental tool has been proposed to identify accurately the layer number and doping type of the FLGs.     

Raman spectroscopic studies of pulsed laser‐induced defect evolution in graphene

Raman spectra were obtained for graphene after irradiating the samples by pulsed laser (λ = 248 nm). Changes in the spectra were observed as the pulse laser energy density (PLED) was varied from 0.1 to 0.25 J/cm². Changes in bilayer graphene were accompanied by the appearance of the D peak and the broadening of the G peak. Changes in multilayer graphene are more profound as the Raman spectra changes from a multilayer to bilayer and subsequently to monolayer graphene in response to a slow increase in the PLED. The threshold PLED was found to be dependent on the number of graphene layers. We also irradiate graphene with very high PLED (much above the threshold), and the Raman spectra were found to be significantly changed. The G‐band became broader, and red shifted, while the intensity of the 2D‐band was drastically reduced and an intense defect‐related D peak appeared at about 1350 cm⁻¹. The laser ablation of graphene, both with low‐ and high‐energy intensity, is consistent with the reported theoretical predictions. Copyright © 2013 John Wiley & Sons, Ltd.     

Excitation energy dependence of Raman bands in multiwalled carbon nanotubes

Vertically aligned multiwalled carbon nanotubes (MWCNTs) were grown on 1‐ and 3‐nm cobalt (Co) films, at various growth times by microwave plasma enhanced chemical vapor deposition technique and their microstructural properties were analyzed with the help of Raman spectra that were obtained from different sources of laser excitation energies (E_L: 2.41, 1.96 and 1.58 eV). The variation of D and G band positions in MWCNTs grown on 1‐ and 3‐nm Co films follows a similar behavior, and an anomalous behavior was observed in the E_L dependence of the D′‐band wavenumber. In the second‐order spectra, the G′ band varied strongly according to structure with the laser excitation energy (E_L). The I_D/I_G ratio decreased with the increase of E_L for all MWCNTs; however, for a fixed E_L, the I_D/I_G dispersion is higher at lower E_L. The crystallite sizes were estimated using I_DI_G and E_L. We have shown that, for all MWCNTs, I_D/I_G ratio is inversely proportional to . Copyright © 2010 John Wiley & Sons, Ltd.     

A statistical analysis of the wavenumbers of triplet rovibronic transitions of the D<Subscript>2</Subscript> molecule: III. Optimum values of level energies

The optimum energy values of the vibrational-rotational levels of all the experimentally studied 35 triplet electronic states of the D2 molecule were found using a one-step optimization procedure only based on the Rydberg-Ritz combination and maximum likelihood principles. The set of energy values for 1050 levels was obtained from 3713 experimental data (3588 old and 125 new data) on the wavenumbers of rovibronic transitions. The energies were counted from the lowest vibrational-rotational level (ν = 0, N = 0) of the (1sσ2sσ)a ³Σ _g ⁺ electronic state. Errors in the empirical determination of optimum level energy values caused only by the limited consistency of the experimental data obtained by different authors, different methods, and in different spectrum regions were found. They are of 0.005–0.1 cm⁻¹ and increase as the vibrational and rotational quantum numbers grow. The possibility of discovery of new not identified earlier band systems was demonstrated. This can be done using the optimum level energies for calculations of the wave-numbers of spectral lines allowed by selection rules followed by the search for these lines in the experimental spectra of D₂.     

Overtone and combination features of G and D peaks in resonance Raman spectroscopy of the C78H26 polycyclic aromatic hydrocarbon

We have studied the Raman spectra of C₇₈H₂₆, a polycyclic aromatic hydrocarbon with D_2h symmetry point group resembling a longitudinally confined graphene ribbon (or a graphene island) with armchair edge. The experimental spectra recorded with several excitation laser lines have been compared with the results from a theoretical analysis of the resonant Raman response based on density functional theory calculations. Compared to previous investigation the spectra show better signal‐to‐noise ratio, which allows determining previously unresolved weak spectroscopic features. We have extended our analysis to the overtone and combination region (i.e. above 2000 cm⁻¹) demonstrating the presence of signals attributable to 2G, G + D, 2D, D_j + D_k and G + acoustic‐like modes. Moreover, we have measured the temperature dependence of the G peak position, which turns out to show a similar behavior with respect to that of graphene/graphite. Copyright © 2015 John Wiley & Sons, Ltd.     

旋转双层石墨烯的电子结构

本文将第一性原理和紧束缚方法结合起来, 研究了层间不同旋转角度对双层石墨烯的电子能带结构和态密度的影响. 分析发现, 旋转双层石墨烯具有线性的电子能量色散关系, 但其费米速度随着旋转角度的减小而降低. 进一步研究其电子能带结构发现, 不同旋转角度的双层石墨烯在M点可能会出现大小不同的的带隙, 而这些能隙会增强双层石墨烯的拉曼模强度, 并由拉曼光谱实验所证实. 通过对比双层石墨烯的晶体结构和电子态密度, 发现M点处带隙来自于晶体结构中的“类AB堆垛区”. 关键词： 旋转双层石墨烯 第一性原理 紧束缚 电子结构     

On the fermi velocity and static conductivity of epitaxial graphene

The models of the energy density of states of a metallic or semiconductor substrate, which does not further lead to divergences, have been proposed to calculate the characteristics of epitaxial graphene. The Fermi velocity of epitaxial graphene formed on a metal has been shown to be greater than that in free-standing graphene irrespective of the position of the Fermi level. On the contrary, the Fermi velocity of graphene formed on a semiconductor is lower so that the lower is the Fermi velocity, the closer is the Fermi level to the center of the band gap of the semiconductor. The zero-temperature static conductivity σ of epitaxial graphene has been calculated according to the Kubo-Greenwood formula. The quantity σ_m of undoped graphene on metal has been shown to decrease with an increase in the deviation of the Dirac point ?_D (which coincides with the Fermi level of the system) from the center of the conduction band of the substrate. In the case of the semiconductor substrate, the static conductivity σ_sc turns out to be nonzero and amounts to σ_sc = 2e ²/π?-only under the condition ?_F =?′_D, where ?′_D is the Dirac-point energy renormalized by the interaction with the substrate.     

Jet Spectroscopy of theD12B1–D01B1Transition of thep-Cyanobenzyl Radical

We have generated thep-cyanobenzyl radical in supersonic free expansion, and measured the vibrationally and rotationally resolved laser induced fluorescence (LIF) excitation spectra and the LIF dispersed spectra from the single vibronic levels (SVL) in the green-blue region. The lowest energy band at 20 738 cm⁻¹with the strongest intensity in the excitation spectrum has been assigned to the 0⁰₀band of the visible spectrum, on the basis of the vibronic structures in the SVL dispersed spectra. Based on the band type of the 0⁰₀band,a-type, determined from the rotationally resolved LIF excitation spectrum, we have definitely assigned the visible band to theD₁2²B₁–D₀1²B₁electronic transition. We have found, on the grounds of the vibrational analysis of the dispersed spectra, that the vibronic structure of the 2²B₁–1²B₁electronic transition of the benzyl type is characterized by totally symmetric fundamental modes, 1, 8a, and 9a.     

Saturation effects on phosphorescence anisotropy measurements at high laser pulse energies

Triplet spectroscopic methods such as time-resolved phosphorescence anisotropy permit successful measurement of slow rotational diffusion of membrane proteins. However, these methods are potentially subject to saturation phenomena. We present theoretical and experimental studies of how high excitation energy densities can complicate measurements of phosphorescence intensity and anisotropy. Increases in excitation laser pulse energy initially increase phosphorescence intensity. Further increases then lead to phosphorescence saturation. As a consequence, the initial phosphorescence anisotropy decreases and approaches zero at very high excitation energies. The relative standard deviation of anisotropies measured in any system reaches a minimum at some particular excitation energy density. These results allow us to define optimum experimental conditions for time-resolved phosphorescence anisotropy measurements. For example, for excitation of erythrosin chromophores at typical wavelengths by the center of a Gaussian laser beam, optimum pulse energies in microjoules are approximately 5.0R ², whereR is the beam 1/e² radius in mm.     

Study of the Superdeformed State of 196Pb in the Relativistic Mean Field Theory

Based on the constrained relativistic mean field (RMF) theory, the superdeformed states of ¹⁹⁶Pb are systematically investigated with four different interactions, TMA, PK1, NL3 and NL-SH. The potential surface, the quadruple deformation of ground and superdeformed states, and the excitation energies of superdeformed states are calculated. The results show that the shape of ¹⁹⁶Pb is oblate for the ground state with deformation β₂≈－0.15, and prolate for the superdeformed states with deformation β₂≈0.60. The calculated excitation energy and the depth of the potential well of the superdeformed state are approximately equal to 4.5MeV and 1.6MeV, respectively. These results are in good agreement with the current experimental data. It indicates that RMF theory can well describe the energy of the band head of superdeformed rotational band in ¹⁹⁶Pb.     

Nonsteady photoconductivity of layers of glass of the As-Se system

This article examines experimental results from a study of impulsive photoconductivity in layers of glasses of As_xSe_100–x (30-@#@ 60). It was found that thermal and laser treatment (thermo- and photostructural changes) affect the character of relaxation processes in photoconduction in freshly prepared layers. It was also established that both annealing at temperatures near the softening point of the glass and laser irradiation with quantum energies exceeding the width of the forbidden band are accompanied by a change in the recombination lifetime of nonequilibrium carriers. It is concluded on the basis of empirical data that an efficient recombination channel complementary to the main channel (tunnel transition of the type 2D⁰D⁺+D^–) is present in freshly prepared layers. The latter is present in annealed layers. The additional recombination channel is related to the existence of homopolar bonds in binary arsenic selenides and is proven to exist by data on the effect of composition on photocurrent relaxation.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 66–71, May, 1987.