Selective resonance enhancement of Raman scattering intensity in photoinduced nonradiative charge transfer

This paper reports on the formation of complexes consisting of isolated free-standing crystalline semiconductor quantum dots, for example, nc-Si/SiO₂, functionalized by short oligonucleotides, for example, the single-stranded system d(20G, 20T). Here, d are deoxyribonucleotides, G and T are guanine and thymine nucleotides, respectively. It has been found that these complexes are unique objects for the elucidation of the specific features in the manifestation of new quantum-size effects in biomacromolecules. It has been demonstrated that the possibility exists of detecting and recording, in such complexes of biomacromolecules, spectrally selective resonance enhancement of Raman scattering intensity in fluctuations of nucleotide molecules due to coherent nonradiative transfer of a photoexcited electron and a hole at the interface of the complex. This dynamic optical imaging of spectral responses can be of applied interest for the development of nanobiophotonic technologies.     

KDP晶体受激拉曼散射特性

详细比较了磷酸二氢钾(KDP)晶体的自发拉曼散射和受激拉曼散射光谱,在受激拉曼散射(SRS)中观察到了自发拉曼散射中最强的振动模的三阶Stokes光(559.43,589.74,623.50nm),由于其他振动模的受激拉曼散射增益系数较小,其SRS光谱未观察到。另外,比较了传统生长的未退火和退火后的KDP晶体及快速生长的锥区和柱区KDP晶体的受激拉曼散射增益系数,结果表明生长方法和热退火对KDP晶体的受激拉曼散射增益系数无明显影响。     

YbVO4晶体的受激拉曼散射

采用腔外单次通过方式,研究了一种新型晶体YbVO4的受激拉曼散射.当抽运激光为532 nm皮秒脉冲时获得了3级斯托克斯线(558.47 nm,587.92 nm,620.67 nm)和1级反斯托克斯线(507.58 nm),测得YbVO4晶体1级斯托克斯受激拉曼散射的稳态增益系数为17.8 4±O.2 cm/Gw,受激拉曼散射的整体转换效率达到37%.实现了YbVO4晶体对355 nm皮秒激光的受激拉曼散射,观察到1级斯托克斯线(366.11 nm),根据抽运阈值得到相应的拉曼增益为29.0±0.3 cm/GW.     

Raman scattering of silver chlorate single crystal

The room temperature Raman spectrum of silver chlorate single crystal have been investigated. We make an assignment of all the optical phonon and separate out the internal and external modes. The observed ClO^-₃ internal modes frequencies closely agree with the values obtained by other authors in different materials.     

LiIO3晶体的受激拉曼散射

 采用腔外单次通过方式,测量了LiIO₃晶体在532 nm皮秒脉冲下的受激拉曼散射。实验中观察到3级斯托克斯线（556.07,582.30, 611.76 nm）和1级反斯托克斯线（509.57 nm）,由此可计算出其频率间隔为820 cm^-1。测量了LiIO₃晶体各级拉曼散射谱线的阈值和增益系数,受激拉曼散射的整体转换效率达到56%。基于LiIO₃晶体实现了皮秒外腔式拉曼激光器的运转,双波长输出总转换效率为27%,最大输出能量1.4 mJ。     

KDP晶体受激拉曼散射特性

详细比较了磷酸二氢钾(KDP)晶体的自发拉曼散射和受激拉曼散射光谱,在受激拉曼散射(SRS)中观察到了自发拉曼散射中最强的振动模的三阶Stokes 光(559.43, 589.74, 623.50 nm),由于其他振动模的受激拉曼散射增益系数较小,其SRS光谱未观察到。另外,比较了传统生长的未退火和退火后的KDP晶体及快速生长的锥区和柱区KDP晶体的受激拉曼散射增益系数,结果表明生长方法和热退火对KDP晶体的受激拉曼散射增益系数无明显影响。     

Direct visual evidence for the chemical mechanism of surface‐enhanced resonance Raman scattering via charge transfer

We describe the chemical and electromagnetic enhancements of surface‐enhanced resonance Raman scattering (SERRS) for the pyridine molecule absorbed on silver clusters, in which different incident wavelength regions are dominated by different enhancement mechanisms. Through visualization we theoretically investigate the charge transfer (CT) between the molecule and the metal cluster, and the charge redistribution (CR) within the metal on the electronic intracluster collective oscillation excitation (EICOE). The CT between the metal and the molecule in the molecule–metal complex is considered as an evidence for chemical enhancement to SERRS. CR within the metal on EICOE is considered as an evidence for the electromagnetic enhancement by collective plasmons. For the incident wavelength from 300 to 1000 nm, the visualized method of charge difference density can classify the different wavelength regions for chemical and electromagnetic enhancement, which are consistent with the formal fragmented experimental studies. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman scattering in a ferroelectric sodium nitrite crystal

Raman spectra of the ferroelectric sodium nitrite are recorded over a wide spectral range at different temperatures, including the ferroelectric phase transition interval. The room-temperature Raman spectrum reveals the overdamped А₁(z) soft mode which is attributed to the ferroelectric phase transition.     

Experimental determination of the charge-transfer exciton band width in anthracene-PMDA crystal

The charge-transfer (CT) exciton is investigated on the reflection and luminescence spectra of isotopically mixed anthracene-PMDA crystals. The observed features are analyzed by the coherent potential approximation. It is concluded that the CT exciton in this crystal has the band width of about 100 cm^?1.     

Atomic and molecular beam scattering from crystal surfaces in the quantum regime

Atomic beam scattering from surfaces is rapidly evolving as a valuable technique for exploring atom-surface interactions, manifested in both elastic and inelastic processes. We review this field with emphasis on the regime of elastic scattering of low mass particles, where quantum effects are apparent. The discussion focuses on recent developments including both experimental and theoretical methods and results. Information about the potential that can be deduced from selective adsorption observations is described.     

KDP晶体拉曼散射角度特性

利用群理论详细分析了磷酸二氢钾(KDP)晶体的拉曼振动模式,得出了其拉曼振动模的归类?并采用拉曼光谱仪测量了Z切退火KDP晶体X(ZZ)X,Z(XY)Z和Y(XY)X三种散射配置和未退火KDP晶体Z(XY)Z配置下的拉曼光谱?根据拉曼选择定则得出X(ZZ)X,Z(XY)Z和Y(XY)X散射配置下的拉曼峰分别对应A1,B2(LO)?B2(TO)对称类振动模,但在Z(XY)Z配置下的拉曼光谱中除了B2模,还观察到了A1模,而在Y(XY)X配置下的拉曼光谱中只有B2模,且退火和未退火晶体Z(XY)Z配置下的拉曼光谱无明显差别,此结果表明KDP晶体的对称性降低,在背向散射时A1模也具有角度特性,但与晶体的内应力无关,这是由KDP晶体内部结构决定的?     

Anomalous surface enhanced molecular Raman scattering from inelastic tunneling spectroscopy junctions

Anomalously strong Raman spectra have been obtained from molecular monolayers adsorbed on the insulator in metal-insulator-metal tunnel junctions. We show unambiguously that Raman spectroscopy can readily detect molecular monolayers and consider the effects of surface roughness, the molecule-metal interface and the metal on our results.     

Raman scattering in the Bi2TeO5 single crystal

Polarized Raman spectra of the Bi₂TeO₅ single crystal have been investigated for the first time. The group-theoretic analysis of the first-order vibrational spectra is performed. The number of the experimentally observed bands is less than the predicted number of normal modes. The spectral ranges with similar bands are revealed. Some ranges in the spectra of Bi₂TeO₅ are identified from the spectral data for the materials containing bismuth-oxygen and tellurium-oxygen complexes.     

The buildup of stimulated Raman scattering from spontaneous Raman scattering

We present a quantum electrodynamic theory which shows for the first time how stimulated Raman scattering builds up, both spatially and temporally, from spontaneous Raman scattering. We analytically solve operator Maxwell-Bloch equations to find the Stokes field operator, and thus the Stokes intensity, for both monochromatic and broad-band (phase diffusion) pump lasers.     

KDP晶体拉曼散射角度特性

利用群理论详细分析了磷酸二氢钾(KDP)晶体的拉曼振动模式,得出了其拉曼振动模的归类。并采用拉曼光谱仪测量了Z切退火KDP晶体X(ZZ)珡X,Z(XY)珚Z和Y(XY)X三种散射配置和未退火KDP晶体Z(XY)珚Z配置下的拉曼光谱。根据拉曼选择定则得出X(ZZ)珡X,Z(XY)珚Z和Y(XY)X散射配置下的拉曼峰分别对应A1,B2(LO),B2(TO)对称类振动模,但在Z(XY)珚Z配置下的拉曼光谱中除了B2模,还观察到了A1模,而在Y(XY)X配置下的拉曼光谱中只有B2模,且退火和未退火晶体Z(XY)珚Z配置下的拉曼光谱无明显差别,此结果表明KDP晶体的对称性降低,在背向散射时A1模也具有角度特性,但与晶体的内应力无关,这是由KDP晶体内部结构决定的。     

Raman scattering from microcrystals

This review discusses the size effects on Raman scattering from microcrystals. For ionic microcrystals, the existence of surface phonon modes is predicted from electromagnetic theories. It is shown that Raman spectroscopy is very effective to detect the surface phonon modes. The size effects on nonpolar phonons in covalent microcrystals can also be studied by Raman spectroscopy. However, the relaxation of the wave-vector selection rule or the phonon confinement explains only some of the experimental data. Development of lattice dynamical theories of Raman scattering from microcrystals including surface effects is highly required. Enhancement of Raman intensities arising from the excitation of electromagnetic normal modes of microcrystals is also discussed.     

Raman spectra of the librational phonon modes in isotopically mixed anthracene-PMDA crystals

Raman spectra have been measured for the librational phonon modes in the charge transfer complex anthracene-PMDA crystals. Utilizing the isotopically mixed crystals, assignments are made for the six librational Raman modes. From the observed isotopic effects of the Raman lines, it is concluded that the dispersions of these librational modes are highly anisotropic along the direction perpendicular to the molecular stack axis.     

Anisotropic charge transfer rates in the scattering of oriented atoms or molecules from surfaces

Atoms or molecules scattered from surfaces can undergo charge transfer to or from the surface during the scattering event. It is proposed that when the incident particle is “prepared” in an excited or ionic state which is oriented with respect to the surface, observable anisotropies in charge transfer rates involving the oriented state should occur. The effect is illustrated with two examples.     

Charge transfer effects in surface enhanced Raman scattering

Surface enhanced Raman scattering (SERS) due to charge transfer interactions between the adsorbed molecule and the metal surface is analyzed using the semiempirical Wolfsberg-Helmholz method¹ to relate the molecule-surface interactions and the resulting charge transfer states to the overlap integrals between the metal conduction-band orbitals and an acceptor or donor molecular orbital of the molecule. Calculations for the model system of ethylene adsorbed on silver (approximated as a simple cubic metal with tight binding wave functions constructed from Ag 5s valence orbitals), with charge-transfer excitation of an electron from the metal to the antibonding ethylene π orbital, show that charge-transfer Raman enhancements of the order of 10 to 1000 are possible if the charge-transfer band is partially resonant with the exciting radiation. The net enhancement is the product of the charge-transfer gain and the electrodynamic enhancement due to plasmon resonances at surface roughness elements. Symmetric vibrations usually will be enhanced substantially more than nonsymmetric ones by charge-transfer because, in contrast to non-resonant Raman scattering, the vibrational coupling is primarily Franck- Condon (due to differences in the equilibrium nuclear configurations of the ground and excited charge transfer states and the resulting nonorthogonality of different vibrational sublevels of these states) rather than Herzberg-Teller (due to vibrationally induced changes in the electronic wave functions). The charge-transfer mechanism is selective with the most enhanced vibrations involving those atoms which experience the greatest change in electron density between the ground and excited charge-transfer state. A recent report of SERS for benzene on platinum,² strongly suggests charge-transfer enhancement because the electromagnetic-field-enhancing plasmon resonances are strongly damped in this metal.The complete paper will be published in the December 1, 1982 issue of the Journal of Chemical Physics.     

Enhanced stimulated Raman scattering in slow-light photonic crystal waveguides

We investigate for the first time, to our knowledge, the enhancement of the stimulated Raman scattering in slow-light silicon-on-insulator (SOI) photonic crystal line defect waveguides. By applying the Bloch-Floquet formalism to the guided modes in a planar photonic crystal, we develop a formalism that relates the intensity of the downshifted Stokes signal to the pump intensity and the modal group velocities. The formalism is then applied to two prospective schemes for enhanced stimulated Raman generation in slow-light photonic crystal waveguides. The results demonstrate a maximum factor of 104(66,000) enhancement with respect to SOI channel waveguides.