Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues

The Raman depolarization ratios for individual Q₁(J”) branch lines of all diatomic hydrogen isotopologues – H₂, HD, D₂, HT, DT, and T₂ – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q₁(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Orientation of sp2 carbon nanoclusters in ion‐implanted polymethylmethacrylate as revealed by polarized Raman spectroscopy

Raman spectroscopy is widely used for the characterization of bonding type in carbon‐based materials, including carbonized surface layer in ion‐implanted polymers. Studies of the polarization properties of Raman scattering from amorphous carbonaceous materials, however, are very scarce. In this paper, we investigate the polarized Raman spectra of polymethylmethacrylate (PMMA) implanted with 50‐keV Si⁺ ions at fluences in the range 3.2 × 10¹⁴–1.0 × 10¹⁷ ions/cm² and for different visible excitation wavelengths. The spectra of the implanted samples are dominated by the D‐ and G‐bands of sp² carbon, which evidence strong carbonization of the ion‐modified layer. The multiwavelength excitation allowed us to resonantly probe the depolarization ratios for sp² clusters of different sizes. We established that the depolarization ratio ρ_G of the G‐band correlates with the sp² cluster size approaching the random orientation limit of 0.75 for the smallest clusters and a limiting value of 0.41 for the largest clusters. The experimental findings give evidence for a preferable orientation of the larger size clusters with their hexagonal planes perpendicular to the surface of the sample. A plausible explanation for such an arrangement is that the sp² clusters form tile‐like arrangements along the ion tracks. This finding may give clues for understanding of the strong transconductance of the ion‐modified layer, and open prospects for the application of polarized Raman spectroscopy as a characterization tool for surface morphology in ion‐implanted materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Compensated Polarization Scrambler for Raman Depolarization and Intensity Measurements on Microsamples

It has long been recognized ^1,2,3,4,5 in measuring relative intensities and depolarization ratios of Raman lines that prism and grating spectrometers have different transmittances for light polarized parallel (T_∥) and perpendicular (T_⊥) to the slit. Several methods have been used to give equal instrument response to parallel and perpendicular polarization. Stitt and Yost³ used a Nicol prism parallel to the high-transmittance direction of the spectrometer, combined with a rotatable mica half-wave plate to transmit either vector to the Nicol prism. This method has the advantage of having a higher spectrometer transmittance, but the mica plate gives exact half-wave retardation at only a single wavelength. A mica quarter-wave plate ^4,5 averages the transmittances of the spectrometer for the two polarization directions, but is also wavelength dependent. Virtually achromatic circular polarizers have been designed and constructed ^6,7, but these devices are too bulky and expensive for the clear apertures needed for fast spectrometers.     

Precise measurement of the depolarization ratio from photoacoustic Raman spectroscopy

A new method for the accurate determination of the Raman depolarization ratio is reported with an improved setup for photoacoustic Raman spectroscopy (PARS). The precise measurement is achieved by measuring the dependence of the acoustic signal intensity on the cross‐angle between the polarizations of two incident laser beams. We demonstrate this sensitive and simple method with several gaseous molecules, such as CH₄ and H₂. The measured results of depolarization ratios agree well with the theoretical values with an upper error limit of ± 0.005, which is comparable to that with polarization‐resolved CARS spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

The resonant secondary emission of the F center in alkali halides

The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states.     

Polarization resolved stimulated raman scattering: probing depolarization ratios of liquids

Polarization resolved stimulated Raman scattering (SRS) signal is described in the case of isotropic media and linearly polarized incident fields. The model gives simple expressions for the two perpendicularly polarized SRS signals I_X and I_Y, detected along the X and Y directions, respectively, as a function of the incident pump and Stokes polarization angles. We find that Raman depolarization ratio can be simply obtained from the ratio of the SRS intensities detected along the X and Y axis. These theoretical findings are supported by polarization resolved SRS measurements performed on polarized and depolarized bands of cyclohexane. Copyright © 2011 John Wiley & Sons, Ltd.     

CCl4拉曼光谱退偏度的分析和测量

本文主要研究了CCl4的拉曼散射光的偏振特性,通过观察和分析其光强分布图,计算出了CCl4的退偏比,并通过和理论计算结果的比较,了解分子结构和振动的对称性与拉曼光谱的偏振特性之闫的关系。     

用CARS技术确定拉曼退偏比的一种数据处理新方法

Yuika等人利用偏振CARS技术可以准确地确定分子的拉曼退偏比.其方法是，首先对不同检偏角_d所对应CARS谱峰的频率分布进行数学模拟，然后由所得系数随检偏角φ_d的变化求得使CARS信号中共振项消失的偏振角φ^０_d，最后由消失条件ρ＝-1/(tanθtanφ⁰_d)求出退偏比ρ，θ为产生CARS光的Pump光与Stokes光偏振方向的夹角.本文提出的数据处理方法，即交点法.同Yuika等人处理数据的方法相比，交点法毋需关于谱峰频率分布的知识，做法也更为简便.     

Fingerprints of the anisotropic spin-split hole dispersion in resonant inelastic light scattering in two-dimensional hole systems

In resonant inelastic light scattering experiments on two-dimensional hole systems in GaAs-Al(x)Ga(1-x)As single quantum wells we find evidence for the strongly anisotropic spin-split hole dispersion at finite in-plane momenta. In all our samples we detect a low-energy spin-density excitation of a few meV, stemming from excitation of holes of the spin-split ground state. The detailed spectral shape of the excitation depends sensitively on the orientations of the linear light polarizations with respect to the in-plane crystal axes. In particular, we observe a doublet structure, which is most pronounced if the polarization of the incident light is parallel to the [110] in-plane direction. Theoretical calculations of the Raman spectra based on a multiband k · p approach confirm that the observed doublet structure is due to the anisotropic spin-split hole dispersion.     

Spin–orbit stiffness of the spin‐polarized electron gas

In a spin‐polarized electron gas, Coulomb interaction couples the spin and motion degrees of freedom to build propagating spin waves. The spin wave stiffness S_sw quantifies the energy cost to trigger such excitation by perturbing the kinetic energy of the electron gas (i.e. putting it in motion). Here we introduce the concept of spin–orbit stiffness, S_so, as the energy necessary to excite a spin wave with a spin polarization induced by spin–orbit coupling. This quantity governs the Coulombic enhancement of the spin–orbit field acting of the spin wave. First‐principles calculations and electronic Raman scattering experiments carried out on a model spin‐polarized electron gas, embedded in a CdMnTe quantum well, demonstrate that S_so = S_sw. Through optical gating of the structure, we demonstrate the reproducible tuning of S_so by a factor of 3, highlighting the great potential of spin–orbit control of spin waves in view of spintronics applications. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Raman scattering from p-benzoquinone

The Raman spectrum of powdered p-benzoquinone and p-benzoquinone-d₄ has been investigated at liquid nitrogen temperature using Kr⁺-laser excitation. Several new lines were observed. To facilitate the assignment, depolarization ratios have been measured in the melt and in acetone solution. Overlapping peaks were resolved with the aid of a computer program.     

Advanced aspects of electromagnetic SERS enhancement factors at a hot spot

In this paper, we discuss some advanced theoretical aspects of electromagnetic enhancement factors (EFs) in surface‐enhanced Raman scattering (SERS). We focus in particular on the influence of surface selection rules (SSRs) on SERS EFs at hot spots, and the determination of SERS depolarization ratios. Both aspects could be viewed as secondary (compared to the overall magnitude of the SERS EF), but are nevertheless observable experimentally and crucial for a fundamental understanding of SERS. They also share the property that they cannot be studied within the commonly used |E | ⁴ approximation to the SERS EFs, and appropriate tools are developed here to make predictions beyond this approximation in the case of a SERS hot spot. In addition, theoretical estimates of different types of (previously defined) EFs are provided, and their origins discussed for the typical example of a SERS substrate dominated by SERS hot spots. Finally, experimental measurements of SERS depolarization ratios are presented to support the theoretical predictions. Copyright © 2008 John Wiley & Sons, Ltd.     

On the relative intensities of the Raman active fundamentals,r0 structural parameters,and pathway of chair–boat interconversion of cyclohexane and cyclohexane‐d12

Raman spectra of liquid cyclohexane, C₆H₁₂, and deuterated cyclohexane, C₆D₁₂, were recorded with both parallel and perpendicular polarizations. The observed vibrational wavenumbers, depolarization ratios, and their intensities were measured and compared with the corresponding predicted values as well as the experimental values previously reported. The conformational energetics were obtained with the Møller–Plesset perturbation method to the second order [MP2(full)] as well as with density functional theory by the B3LYP method utilizing a variety of basis sets. The average ab initio predicted difference in energy between the more stable chair form (D_3d) and the less stable twisted‐boat form (D₂) is 2213 cm⁻¹ (26.47 kJ/mol), with a similar value of 2223 cm⁻¹ (26.59 kJ/mol) from the density function theory calculations. By using two dihedral angles as variables, we calculated the chair–boat interconversion pathway for cyclohexane at the MP2(full)/6‐31G(d) level. The harmonic force constants, Raman intensities, depolarization values, and the potential energy distribution were predicted from both MP2(full) and B3LYP calculations with the 6‐31G(d) basis set and compared with the experimental values for the chair form when available. The ‘adjusted’ r₀ structural parameters were obtained from MP2/6‐311 + G(d,p) calculations and previously reported microwave rotational constants of five isotopomers of cyclohexane: i.e. 1,1‐d₂, ¹³C‐1,1‐d₂, 1,1,2,2,3,3‐d₆, and d₁ (equatorial and axial). The determined distances in Å are: r(CC) = 1.536(3), r(CH)_ax = 1.098(1); r(CH)_eq = 1.095(1); and the angles in degrees: ∠CCH_ax = 108.8(3); ∠CCH_eq = 110.2(3); ∠CCC = 111.1(3); and ∠HCH = 107.6(3) with dihedral angle ∠CCCC = 55.7(3). These values are compared with those previously reported and it is found that the difference in the r₀ distances (0.003 Å) between the two CH values is much smaller than the difference (0.008 Å) previously reported for the r_s values. Copyright © 2008 John Wiley & Sons, Ltd.     

Probing the structure and Franck–Condon region of protochlorophyllide a through analysis of the Raman and resonance Raman spectra

The structure and Franck–Condon region of protochlorophyllide a, a precursor in the biosynthesis of chlorophyll and substrate of the light‐regulated enzyme protochlorophyllide oxidoreductase (POR), were investigated by Raman and resonance Raman (RR) spectroscopy. The spectroscopic results are compared to the spectra of the structurally closely related porphyrin model compound magnesium octaethylporphyrin (MgOEP), and interpreted on the basis of density functional theory (DFT) calculations. It is shown that the electronic properties of the two porphyrin macrocycles are affected by different vibrational coupling modes, resulting in a higher absorption cross section of protochlorophyllide a in the visible spectral region. Furthermore, a comparison of the Fourier transform (FT)‐Raman and RR spectra of protochlorophyllide a indicates the modes that are resonantly enhanced upon excitation. Based on vibrational normal mode calculations, these modes include C C ring‐breathing and CC stretching vibrations of the porphyrin macrocycle. In particular, the strong band at 1703 cm⁻¹ can be attributed to the CO carbonyl vibration of the cyclopentanone ring, which is attached in conjugation to the π‐electron path of the porphyrin ring system. The enhancement of that mode upon electronically resonant excitation is discussed in the light of the reaction model suggested for the photoreduction of protochlorophyllide a in the POR. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural dynamics of 4‐formaldehyde imidazole and imidazole in light absorbing S2(ππ*) state

The short‐time structural dynamics of 4‐formaldehyde imidazole and imidazole in light absorbing S₂(ππ*) state were studied by using resonance Raman spectroscopy and quantum mechanical calculations. The vibrational spectra and ultraviolet absorption spectra of 4‐formaldehyde imidazole were assigned. The resonance Raman spectra of imidazole and 4‐formaldehyde imidazole were obtained in methanol and acetonitrile with excitation wavelengths in resonance with the first intense absorption band to probe the short‐time structural dynamics. complete active space self‐consistent field calculations were carried out to determine the minimal singlet excitation energies and structures of S₁(nπ*), S₂(ππ*), and conical intersection point S₁(nπ*)/S₂(ππ*). The results show that the A‐band structural dynamics of imidazole is predominantly along the N₁H/C₄H/C₅H/C₂H in‐plane bending reaction coordinate, which suggests that excited state proton or hydrogen transfer reaction takes place somewhere nearby the Franck–Condon region. The significant difference in the short‐time structural dynamics between 4‐formaldehyde imidazole and imidazole is observed, and the underlying mechanism is interpreted in term of excited state charge redistribution. Copyright © 2015 John Wiley & Sons, Ltd.     

Experimentally validated Raman Monte Carlo simulation for a cuboid object to obtain Raman spectroscopic signatures for hidden material

In conventional Raman spectroscopic measurements of liquids or surfaces the preferred geometry for detection of the Raman signal is the backscattering (or reflection) mode. For non‐transparent layered materials, sub‐surface Raman signals have been retrieved using spatially offset Raman spectroscopy (SORS), usually with light collection in the same plane as the point of excitation. However, as a result of multiple scattering in a turbid medium, Raman photons will be emitted in all directions. In this study, Monte Carlo simulations for a three‐dimensional layered sample with finite geometry have been performed to confirm the detectability of Raman signals at all angles and at all sides of the object. We considered a non‐transparent cuboid container (high density polyethylene) with explosive material (ammonium nitrate) inside. The simulation results were validated with experimental Raman intensities. Monte Carlo simulation results reveal that the ratio of sub‐surface to surface signals improves at geometries other than backscattering. In addition, we demonstrate through simulations the effects of the absorption and scattering coefficients of the layers, and that of the diameter of the excitation beam. The advantage of collecting light from all possible 4π angles, over other collection modes, is that this technique is not geometry specific and molecular identification of layers underneath non‐transparent surfaces can be obtained with minimal interference from the surface layer. To what extent all sides of the object will contribute to the total signal will depend on the absorption and scattering coefficients and the physical dimensions. Copyright © 2015 John Wiley & Sons, Ltd.     

Analysis of G‐quadruplex conformations using Raman and polarized Raman spectroscopy

G‐quadruplexes (G4s) are four‐stranded DNA structures formed within nucleic acid sequences that are rich in guanines. G4 formation within DNA strands is believed to have significant biological relevance for the control of cell replication and gene expression. Therefore, the development and validation of experimental techniques that can easily and reliably characterize G4 structures under biologically relevant measurement conditions, like Raman spectroscopy, are desirable for G4‐targeted structure based drug design. Here we report Raman and polarized Raman studies of solutions of three oligonucleotides, thrombin binding aptamer (TBA) 5′‐GGTTGGTGTGGTTGG‐3′, human telomeric (HT) 5′‐(TTAGGG)₄‐3′, and a modified c‐Myc NHE‐III₁ sequence (MycL1) 5′‐TGAGGGTGGGTAGGGTGGGTAA‐3′, which were previously reported to form four distinct intramolecular G4 structures in the presence of Na⁺ or K⁺, as determined by NMR. Our results support the previously proposed antiparallel (TBA), antiparallel and hybrid (HT), and parallel with double‐chain reversal (DCR) loop (MycL1) structures. Large sample‐dependent variations in the intensity of bands associated with deoxyribose backbone modes in the 840–930 cm⁻¹ and 1420–1460 cm⁻¹ spectral regions were observed. Most notably, a highly polarized deoxyribose ring symmetric stretch (~930 cm⁻¹) appeared strongly in the solution spectra for HT and TBA, but was very weak or absent in the solution spectrum for MycL1 and the drop deposition (dried sample) spectra for all three oligonucleotides. It is hypothesized that the intensity of this band is likely controlled by furanose ring structure uniformity and/or solvent accessibility to certain nucleotide binding sites. Raman depolarization ratios measured for the G4s in solution were generally very similar to those previously reported for canonical B DNA, with the possible exception of base ring modes that consistently yielded slightly lower depolarization ratios for G4s compared to B DNA. The results further underscore the utility of Raman and polarized Raman spectroscopy for G4 structure elucidation under biologically relevant solution conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

STUDY OF BRANCHING RATIONS OF 3p3/2nd (J=1,3) AUTOIONIZING SERIES OF NEUTRAL MAGNESIUM

With the K matrix and multichannel quantum defect theory, we have studied the branching ratios of 3p_3/2nd (J=1,3) autoionizing series of Mg above the 3p_1/2 ion limit. The calculations are compared with the previous experimental spectra, and the unmeasured branching ratios are presented. The conclusion is that 3p_3/2nd state prepared by the three-step excitation can form population inversion between the 3p_1/2 and 3s_1/2 ionic states.     

Polarized raman spectroscopy on isolated single-wall carbon nanotubes

Polarized micro-Raman spectroscopy has been performed on spatially separated single-wall carbon nanotubes (SWNTs) in the form of individual nanotubes or thin ropes of only a few SWNTs. Different from bulk samples, the Raman spectra are composed of well-resolved peaks which allow a direct comparison of experimental data with theoretical calculations. Orientation-dependent measurements reveal maximum intensity of all Raman modes when the nanotubes are aligned parallel to the polarization of the incident laser light. The angular dependences clearly deviate from the selection rules predicted by theoretical studies. These differences are attributed to depolarization effects caused by the strongly anisotropic geometry of the nanotubes and to electronic resonance effects for excitation at 633 nm.     

First evidence for vibrational excitations of large atomic clusters in amorphous semiconductors

Raman and depolarization spectra of GeSe₂ alloyed with Se or As₂Se reveal a sharp vibrational doublet, only one component of which can be attributed to a vibrational excitation of the GeSe₂ local atomic cluster. The composition dependence of the intensity and polarization of the second feature identify it as an excitation involving a substantially larger cluster with high symmetry. The large cluster is a ring of Ge atoms inter-connected through single Se atoms