Electron paramagnetic resonance and photoluminescence properties of α-Al2O3:Cr3+ phosphors

The red emitting Cr³⁺ activated α-Al₂O₃ powder phosphor has been prepared by easy combustion reactions from mixed metal nitrate reactants and urea with ignition temperatures of 500 °C. The as-synthesized powder was characterized by X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared techniques. The X-ray diffraction pattern reveals that the phosphor crystallized in the hexagonal α-Al₂O₃ phase directly from the combustion reaction. The EPR spectrum exhibits an intense resonance signal with effective g value at g=3.33 along with a few weak resonance signals with effective g values at g=13.7, 2.34, 1.95, 1.49, and 1.26. The spin concentration (N) and its paramagnetic susceptibility (χ) have been evaluated. The excitation spectrum consists of two broad intense bands at 415 nm and 555 nm and are assigned to ⁴A_2g (F)→⁴T_1g (F) and ⁴A_2g (F)→⁴T_2g (F) transitions, respectively. The intense fluorescence peak around 691 nm is attributed to ²E _g →⁴A_2g transition of Cr³⁺ ion. By correlating EPR and optical data, the crystal field splitting parameter (Dq), Racah inter-electronic repulsion parameter (B) have been evaluated and discussed. The EPR and optical studies reveal that Cr³⁺ ions are occupying in Al³⁺ sites in octahedral coordination.     

Exciton-magnon interactions in NicMg1−c O single crystals

The effect of chemical composition and temperature on exciton-magnon interactions in Ni_cMg_1?c O single crystals was studied using optical absorption spectra in the region of the magnetic-dipole ³ A _2g (G)→³ T _2g (F) and electric-dipole ³ A _2g (F)→¹ E _g (D) transitions. The two zero-phonon lines at ～7800 and ～7840 cm^?1 on the low-energy side of the magnetic-dipole transition band were assigned to a pure exciton transition and an exciton-one-magnon transition at the center of the Brillouin zone. The intensity of the exciton-one-magnon peak decreases rapidly with increasing magnesium ion concentration and/or temperature, to vanish altogether at T=6 K for c<0.95 and at T=130 K for c≥0.99. Thus, the contribution of long-wavelength magnons in optical absorption spectra of Ni_cMg_1?c O becomes negligible at temperatures substantially lower than the Néel point T _N (the antiferromagnetic ordering temperature). This observation can be explained as being due to a substantial decrease in the characteristic spin-spin interaction length with increasing concentration of the diamagnetic magnesium impurity ions (static disorder) and/or with increasing amplitude of thermal atomic vibrations (dynamic disorder). At the same time, the peak at ～14500 cm^?1, which lies in the electric-dipole transition region and corresponds to excitation of an exciton and two magnons at the Brillouin zone edge, remains visible up to the Néel temperature. This is accounted for by the short-wavelength magnons being sensitive to short-range magnetic order, which persists up to T _N .     

On the theory of Boson peak in glasses

A universal mechanism of the Boson peak formation in glasses is proposed. The mechanism is based on the concept of interacting quasilocal oscillators. Even in the case of weak interaction, the low-frequency spectrum becomes unstable. Due to anharmonicity, the system undergoes a transition into a new stable configuration. As a result, below some characteristic frequency ω_c, proportional to the typical strength of interaction, the renormalized density of states becomes a universal function of ω with a Boson peak feature; i.e., the reduced density of states g(ω)/ω² has a maximum at a frequency ω_b?ω_c. We derive an analytic form of this function.     

Third-order optical harmonic coefficients of atomic hydrogen at low frequencies

The analytical expression is derived for the third-order optical harmonic coefficients χ⁽³⁾₁₁₁₁ (ω, ω, ω) = χ⁽³⁾₂₂₂₂ (ω, ω, ω) = χ⁽³⁾₃₃₃₃ (ω, ω, ω) of the atomic hydrogen at very low frequencies ω → 0.     

Nonlinear susceptibilities of vapors and solutions of organic dyes

Results of theoretical studies of laser and Kerr nonlinear susceptibilities of vapors and solutions of organic dyes using a series of polycyclic arenes as an example are presented. Nonlinear susceptibilities of the third χ⁽³⁾ (?3ω; ω, ω, ω) and the fifth χ⁽⁵⁾ (?3ω; ω, ω, ω, ω, ?ω) orders of a series of organic dyes responsible for third harmonic generation of Nd:YAG laser radiation are calculated within the context of the free electron model. Results of calculations of their Kerr third-order nonlinear susceptibilities χ⁽³⁾ (?ω; ω, ?ω, ω) and non-linear refractive indices n ₂ are presented. The calculation results are compared with experimental data on third harmonic generation in naphthalene vapors and with χ⁽³⁾ (?ω; ω, ?ω, ω) as well as n ₂ of paraterphenyl and naphthalene solutions.     

Third-order nonlinear optical response in double-walled carbon nanotubes

Resonant behavior and magnitudes of third-order nonlinear optical susceptibilities in double-walled carbon nanotubes (DWNTs) have been investigated by means of femtosecond pump-probe spectroscopy with different pump-photon energies. With the selective excitation of the E₂₂ exciton transition of the inner tubes labeled by the chiral vector indices (7,5) and (7,6), the imaginary part of nonlinear susceptibility Imχ⁽³⁾ has shown the resonant enhancement compared with the case of the nonresonant excitation of the specific tube. The nonlinear response signal at the E₂₂ transition energy of the (8,7) tube has been also enhanced for the excitation of the G-band phonon sideband of its E₂₂ transition. This result is consistent with the phonon-mediated nonlinear optical process observed for the E₂₂ transitions in single-walled carbon nanotubes (SWNTs). It has been also found that the values of the figure of merit Im χ⁽³⁾/α (α: absorption coefficient) of the inner tubes in DWNTs are smaller than those of the corresponding SWNTs, which is interpreted in terms of decay time shortening due to the energy relaxation between the inner and outer tubes.     

Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.     

The D′ → A′ transition in I2

A detailed vibrational analysis is given for the D′(2g) → A′(2u³Π) transition (3300–3460 Å) in I₂. The assignments include ～ 150 v′-v″ bands in ¹²⁷I₂ and ～100 in ¹²⁹I₂, spanning v′ levels 0–15 and v″ levels 4–30. These bands are mainly red-degraded but include some violet-degraded and line-like features. The analysis is corroborated by Franck-Condon and band profile calculations. The least-squares fit yields the following constants (cm^?1); ΔT_c = 30 340.8, ω′_e = 103.95, ω_eχ′_e = 0.206, ω″_e = 106.1, ω_eχ″_e = 0.81. Anomalous behavior in the vibrational level structure above v″ = 23 makes the extrapolation to the A′ dissociation limit uncertain, so the absolute energies of both states remain ill-defined. However there is a possibility that the D′ state is the state labeled α by King et al. [Chem. Phys. 56, 145–156 (1981)], in which case the energies are known precisely. There is evidence of weak emission from at least two other electronic transitions in this spectral region, probably $\text{D(0}{}^{\mathrm{+}}\text{u) → X(}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ ($\text{λ}\text{< 3300}\text{A}\text{?}$) and β → A(1u³Π) ($\text{λ}\text{> 3300}\text{A}\text{?}$).     

The exciton absorption in deformed germanium

Absorption spectra at 77° K near the direct (κ = 0) exciton transition are reported for deformed and undeformed single-crystal films of n-type Ge oriented on (111); Elliott's theory is applied. The optical width of the forbidden band for this transition is found as E_{g 0} = (0.8821 ±±0.0002) eV, while the exciton binding energy is found as E_ex(0) = = (0.0016±0.0003) eV for undeformed Ge at 77 ° K. The mean temperature coefficient of E_g for κ = 0 in the range 77 °–297 ° K is (dE_g/ /dT)_p =?3.50 · 10^?4 eV/deg. The effects of thermoelastic deformation on the exciton spectrum give (dE_g/dT)_d = (?1.5±0.1) · 10^?4 eV/deg. The half-width σ ≈ 5 · 10^?4 eV of the exciton peak gives the exciton lifetime as gt ≥ 10^?12 sec.     

Phonons in disordered solids

The effects of crystalline disorder on the frequency distribution and lifetimes of phonons are investigated. As the disorder parameter g characterizing the scattering of normal modes is increased to g>g_c, the normal mode spectrum becomes unstable against arbitrarily small nonlinearities while the ground state (if any) becomes increasingly degenerate. The bandwidth of the acoustic phonon spectrum increases with g, from a value ω_Dat g = 0 to 1.24ω_D at g_c. The speed of sound at long wavelengths decreases with increasing g; at threshold (g_c) it has decreased by some 29.3% from its value at g = 0. For g < g_c the scattering lifetime of long-wavelength normal modes satisfies Rayleigh's law (1/τ = A(_g)ω⁴). At g_c the damping satisfies a different law: 1/τ = Bω². Similar effects are obtained for the optic mode phonons. For these reasons, it appears that g_c marks the threshold of amorphous behavior, although the regime g >g_c is beyond the scope of our model.     

Cerussite,PbCO3 – a new Stimulated Raman Scattering (SRS)‐active crystal with high‐order Stokes and anti‐Stokes lasing

Orthorhombic PbCO₃, known as natural crystal cerussite, is presented as a new Stimulated Raman Scattering (SRS)‐active crystal. With picosecond laser pumping high‐order Raman‐induced χ⁽³⁾ generation is observed. All registered Stokes and anti‐Stokes sidebands in the visible and near‐IR are identified and attributed to the SRS‐promoting phonon mode A_1g of the carbonate group, with ω_SRS ≈ 1054 cm⁻¹. The first Stokes steady‐state Raman gain coefficient in the visible spectral range is estimated as well to a value not less than 4.6 cm·GW⁻¹.     

Multiphoton SRS-Lasing in a Monoclinic β-BaYb<Subscript>2</Subscript>F<Subscript>8</Subscript> Crystal

The discovery of stimulated Raman scattering (SRS) in monoclinic fluoride β-BaYb₂F₈ known as a host matrix for Ln³⁺ lasant ions was reported. All the recorded spectral components of Stokes and anti-Stokes χ⁽³⁾-nonlinear picosecond generation were assigned to the three SRS-active photon A_g- and B_g-modes of a crystal (ω_SRS1 ~ 362 cm^–1, ω_SRS2 ~ 295 cm^–1, and ω_SRS3 ~ 230 cm^–1).     

Frequency dependence of the large,electronic χ(3) in polyacetylene

The third order optical susceptibilities (χ⁽³⁾) of trans- and cis- (CH)_x have been determined in the spectral region below the gap by measuring the third harmonic generation efficiency. The magnitude of χ⁽³⁾ parallel to the polymer chains in trans-(CH)_x is in excess of 10⁻⁹ esu for wavelengths larger than 1.3 μm, and the spectrum of χ⁽³⁾ in trans-(CH)_x has a sharp two-photon resonance at an energy corresponding to half the semiconducting gap. Both the off resonance and the two-phonon resonance enhanced values of χ⁽³⁾ are explained by a simple band picture.     

Extinction coefficients of carbon grains in far-infrared

With a simple model it is shown that the wavelength-dependence of the extinction of crystalline and amorphous carbon grains in the FIR region is caused by the vibrational density of states g_c(ω) and g_d(ω), respectively. Both are approximated by the well known expressions of the model of the linear chain and the susceptibilities in the FIR are calculated by the equation of Kubo. The result is that the extinction in FIR of the crystalline carbon grains has a λ⁻²-dependence and the amorphous modification has a λ⁻¹-dependence. The results are compared with laboratory measurements, astrophysical observations and other theoretical models.     

Photothermal ionization via excited states of sulfur donor in silicon

Structures in the photoionization cross-section spectra below the extrinsic edge of the doubly charged sulfur donor (613 meV) are attributed to the two-step photothermal excitation process in which the bound electron at the ground state first makes an optical transition to an excited state and it is then thermally released from the excited state to the conduction band. A weak peak (cross-section 7 × 10⁻¹⁹ cm²)at 425 meV is attributed to the intervalley optical transition 1s(A₁)→1s(T₂). Peak observed at 570 meV (10⁻¹⁷ cm²) is attributed to the 1s(A₁→2p₀ intervalley optical transition and the peak at 591 meV (3 × 10⁻¹⁷ cm²) to the 1s(A₁)→2p± intravalley optical transition. Data for electron bound at the neutral gold center has no structures which is consistent with the lack of excited states of a neutral impurity potential.     

Electroabsorption in TlInS2

Electroabsorption spectra of single crystals have been studied near the fundamental absorption edge at 77 and 300 K. At 300 K two positive peaks (2.34 and 2.42 eV) and a negative peak (2.38 eV) are observed in the electroabsorption spectrum. At liquid-nitrogen temperature a fine structure corresponding to the formation of a parabolic exciton (2.503 eV) is observed.Values of the width of the forbidden gap E_g, the n = 1 exciton positions, the exciton activation energy ΔE_b, the effective Bohr radius a_exc, the reduced effective mass of an electron-hole pair μ, and the exciton ionization field F(E_g = 2.535 eV, E_exc = 2.503 eV, E_b = 32 meV, $\text{a}{}_{\mathrm{<mtext>exc</mtext>}}\text{=}\text{28}\text{A}\text{A;}\text{;}$;, μ = 0.15 m₀, and F = 1.2 × 10⁵ V cm^-1) have been determined from the electroabsorption spectrum.     

What is measured in a time-resolved stimulated Raman experiment?

We have performed four-beam time-resolved stimulated Raman measurements on liquid CS₂. To interpret our results we have applied the response formalism for the third-order polarization to such an experiment. It turns out that the measured quantity is proportional to (a convolution of) Abs[χ⁽³⁾(-ω_s, ω_s, ω_l, -ω_l)]. As a consequence in this four-beam e xperiment one picks up electronic contributions in contrast to a two-beam experiment where Im[χ⁽³⁾] is observed.     

An improved technique for the measurement of the complex susceptibility of magnetic colloids in the microwave region

Measurements by means of the short-circuit (S/C) and open circuit (O/C) transmission line techniques are well established methods for investigating the magnetic and dielectric properties of magnetic colloids, respectively. In particular, the S/C technique has been used in the investigation of the resonant properties of ferrofluids; resonance being indicated by the transition of the real component of the magnetic complex susceptibility, χ(ω)=χ′(ω)−iχ″(ω), from a positive to a negative value at a frequency, f_res. However, under certain circumstances, the accuracy of the S/C technique is affected by the dielectric properties of the sample, hence incurring errors in the measurement of χ(ω) and indeed of f_res. Here we present a model which, by combining short-circuit and open circuit measurements, is developed in a manner in which the permeability, μ, and the permittivity, ε, contribute simultaneously to the calculation of χ(ω), thereby providing superior experimental results in comparison to those obtained by the S/C technique alone. For the two ferrofluid samples measured it is demonstrated that the dielectric properties affect the high frequency content of the susceptibility spectrum.     

Heat capacity and low-frequency vibrational density of states. Inferences for the boson peak of silica and alkali silicate glasses

A simple method is used to determine in an absolute way the low-frequency part of the vibrational density of states, g(ω), from inversion of low-temperature heat capacities of glasses. Calculations have been made from adiabatic measurements performed from 10 to 300 K for vitreous SiO₂ and a series of Li, Na and K silicate glasses with up to 50 mol% metal oxide. In all cases, the calculated low-frequency feature is made up of two bands whose maxima lie between 100 and 140 cm⁻¹ and near 400 cm⁻¹. Both the frequency and intensity of the first peak of g(ω) increase linearly with metal oxide content from pure SiO₂ to the metasilicate stoichiometry, reflecting weaker bonding with nonbridging oxygens in the order Li, Na, K, i.e., in order of increasing cationic radius and mass. As represented by the peaks found below 50 cm⁻¹ in plots of g(ω)/ω² vs. ω and below 20 K in plots of C_p/T³ vs. T, the boson peak varies in a different way with composition. Its intensity increases with increasing polymerization for Li and Na silicates whereas the converse holds true for K silicates. These variations agree with the enhancement of the contribution of floppy modes and transverse acoustic modes to the low-frequency vibrational density of states that has previously been reported, but they also point to the importance of localized vibrations in which network modifier cations participate. For either the first peak of g(ω) or the boson peak, however, the size of the alkali cation exerts a stronger influence than the degree of polymerization of the anionic framework. Finally, the universal phenomenology of the boson peak is borne out by the collapse of the calorimetric data on a single master curve when one plots the measurements in a reduced form by using the intensity and position of the peaks as scaling parameters.     

Theory for the nonlinear optical response at noble-metal surfaces with nonequilibrium electrons

We present a theory for the electron-temperature dependence T _el of optical second harmonic generation (SHG). Such an analysis is required to study the dynamics of metallic systems with many hot electrons not at equilibrium with the lattice. Using a tight-binding theory for the nonlinear susceptibility χ ⁽²⁾(ω,T _e1) and the Fresnel coefficients we present results for the SHG intensity I ⁽²⁾(ω,T _e1) and its dependence on T _el for Cu. Note, χ ⁽²⁾(ω,T _e1) rather than the Fresnel coefficients determines essentially this temperature dependence. Most interestingly we find frequency ranges where I ⁽²⁾(ω,T _e1) increases for small light intensities, while it decreases for large light intensities. Our theory yields also that SHG probes effects due to hot electrons more sensitively than linear optics. The results of our calculations are compared with recent experiments on Cu and Au.