Structural origin and energy transfer processes of 1.8 μm emission in Tm3+ doped germanate glasses

A detailed characterization of structural analysis and energy transfer (ET) process in Tm(3+) doped germanate glasses has been presented. The thermal stability and Raman spectroscopic analysis of the host glass structure has been discussed. It is observed that replacing GeO(2) by Ga(2)O(3) resulted in decreasing of glass transition temperature and largest phonon energy. Increasing concentration of Ga(2)O(3) decreases the density of cross-linking of the germanate glass network, and weaker Ga-O bonds result in lower phonon energy. The influences of the concentrations of Ga(2)O(3) and the glass structure on the ET have also been analyzed. The extended overlap integral method is used to calculate the microparameters of the energy transfer and the critical distance. The results show that the transference Tm → Tm ((3)H(4), (3)H(6) → (3)H(6), (3)H(4)) energy migration is not phonon dependent in the quasiresonant processes, while the cross relaxation Tm → Tm ((3)H(4), (3)H(6) → (3)F(4), (3)F(4)) is a multiphonon mechanism dominated by one-phonon creation (～96%). It is demonstrated that the stretching frequencies and the ET processes become lower when increasing the concentration of Ga(2)O(3).     

Spectroscopic investigations of Nd(3+)-doped alkali chloroborophosphate glasses

Optical absorption spectra were studied in wavelength region 400-900 nm for the Nd(3+)-doped alkali (R = Li, Na and K) chloroborophosphate glasses at room temperature. The energy level scheme of the 4f(3) electron configuration was deduced from the observed energy level data using a parametrized Hamiltonian (H(F1)) model which includes 20 free-ion interaction parameters. Reasonable correlation was obtained between the experimental and calculated energy levels. The Judd-Ofelt model for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Omega(2), Omega(4) and Omega(6) for each glass. Using these parameters, the total radiative transition rates (A(T)), non-radiative relaxation rates (W(NR)), branching ratios (beta(R)), integrated cross-sections for the stimulated emission (Sigma), excited state emission intensities (f(ESE)) and excited state absorption intensities (f(ESA)) have been theoretically calculated for certain excited Nd(3+) fluorescent levels. From the results obtained, the conclusion is made about the possibility of using these glasses as laser media.     

Spectroscopic investigations of Nd3+ doped flouro- and chloro-borate glasses

Spectroscopic and physical properties of Nd(3+) doped sodium lead flouro- and chloro-borate glasses of the type 20NaX-30PbO-49.5B(2)O(3)-0.5Nd(2)O(3) (X=F and Cl) have been investigated. Optical absorption spectra have been used to determine the Slater Condon (F(2), F(4), and F(6)), spin orbit xi(4f) and Racah parameters (E(1), E(2), and E(3)). The oscillator strengths and the intensity parameters Omega(2), Omega(4) and Omega(6) have been determined by the Judd-Ofelt theory, which in turn provide the radiative transition probability (A), total transition probability (A(T)), radiative lifetime (tau(R)) and branching ratio (beta) for the fluorescent level (4)F(3/2). The lasing efficiency of the prepared glasses has been characterized by the spectroscopic quality factor (Omega(4)/Omega(6)), the value of which is in the range of 0.2-1.5, typical for Nd(3+) in different laser hosts. Nephelauxetic effect results in a red shift in the energy levels of Nd(3+) for chloroborate glass. The radiative transition probability of the potential lasing transition (4)F(3/2)-->(4)I(11/2) of Nd(3+) ions is found to be higher for flouroborate as compared to chloroborate glass.     

Rotational and vibrational relaxation of methane excited to 2nu3 in CH4/H2 and CH4/He mixtures at 296 and 193 K from double-resonance measurements

A series of time-resolved IR-IR double-resonance experiments have been conducted where methane molecules are excited into a selected rovibrational level of the 2nu3(F2) vibrational substate of the tetradecad and where the time evolution of the population of the various energy levels is probed by a tunable continuous wave laser. The rotational relaxation and vibrational energy transfer processes occurring in methane upon inelastic CH4-H2 and CH4-He collisions have been investigated by this technique at room temperature and at 193 K. By probing transitions in which either the lower or the upper level is the laser-excited level, rotational depopulation rates in the 2nu3(F2) substate were measured. The rate constants for CH4-H2 collisions were found to be 17.7 +/- 2.0 and 18.9 +/- 2.0 micros(-1) Torr(-1) at 296 and 193 K, respectively, and for CH(4)-He collisions they are 12.1 +/- 1.5 and 16.0 +/- 2.0 micros(-1) Torr(-1) at the same temperatures. The vibrational relaxation was investigated by probing other stretching transitions such as 2nu3(F2) - nu3, nu3 + 2nu4 - 2nu4, and nu3 + nu4 - nu4. A kinetic model, taking into account the main collisional processes connecting energy levels up to 6000 cm(-1), that has been developed to describe the various relaxation pathways allowed us to calculate the temporal evolution of populations in these levels and to simulate double-resonance signals. The different rate coefficients of the vibrational relaxation processes involved in these mixtures were determined by fitting simulated signals to the observed signals corresponding to assigned transitions. For vibration to translation energy transfer processes, hydrogen is a much more efficient collision partner than helium, nitrogen, or methane itself at 193 K as well as at room temperature.     

Determination of the rate constant for the NH2(X2B1) + NH2(X2B1) recombination reaction with collision partners He, Ne, Ar, and N2 at low pressures and 296 K. Part 1

The recombination rate constant for the NH(2)(X(2)B(1)) + NH(2)(X(2)B(1)) → N(2)H(4)(X(1)A(1)) reaction in He, Ne, Ar, and N(2) was measured over the pressure range 1-20 Torr at a temperature of 296 K. The NH(2) radical was produced by 193 nm laser photolysis of NH(3) dilute in the third-body gas. The production of NH(2) and the loss of NH(3) were monitored by high-resolution continuous-wave absorption spectroscopy: NH(2) on the (1)2(21) ← (1)3(31) rotational transition of the (0,7,0)A(2)A(1) ← (0,0,0) X(2)B(1) vibronic band and NH(3) on either inversion doublet of the (q)Q(3)(3) rotational transition of the ν(1) fundamental. Both species were detected simultaneously following the photolysis laser pulse. The broader Doppler width of the NH(2) spectral transition allowed temporal concentration measurements to be extended up to 20 Torr before pressure broadening effects became significant. Fall-off behavior was identified and the bimolecular rate constants for each collision partner were fit to a simple Troe form defined by the parameters, k(0), k(inf), and F(cent). This work is the first part of a two part series in which part 2 will discuss the measurements with more efficient energy transfer collision partners CH(4), C(2)H(6), CO(2), CF(4), and SF(6). The pressure range was too limited to extract any new information on k(inf), and k(inf) was taken from the theoretical calculations of Klippenstein et al. (J. Phys. Chem A 2009, 113, 10241) as k(inf) = 7.9 × 10(-11) cm(3) molecule(-1) s(-1) at 296 K. The individual Troe parameters were: He, k(0) = 2.8 × 10(-29) and F(cent) = 0.47; Ne, k(0) = 2.7 × 10(-29) and F(cent) = 0.34; Ar, k(0) = 4.4 × 10(-29) and F(cent) = 0.41; N(2), k(0) = 5.7 × 10(-29) and F(cent) = 0.61, with units cm(6) molecule(-2) s(-1) for k(0). In the case of N(2) as the third body, it was possible to measure the recombination rate constant for the NH(2) + H reaction near 20 Torr total pressure. The pure three-body recombination rate constant was (2.3 ± 0.55) × 10(-30) cm(6) molecule(-2) s(-1), where the uncertainty is the total experimental uncertainty including systematic errors at the 2σ level of confidence.     

Low-melting, low-viscous, hydrophobic ionic liquids: aliphatic quaternary ammonium salts with perfluoroalkyltrifluoroborates

A novel class of low-melting, hydrophobic ionic liquids based on relatively small aliphatic quaternary ammonium cations ([R(1)R(2)R(3)NR](+), wherein R(1), R(2), R(3) = CH(3) or C(2)H(5), R = n-C(3)H(7), n-C(4)H(9), CH(2)CH(2)OCH(3)) and perfluoroalkyltrifluoroborate anions ([R(F)BF(3)](-), R(F) = CF(3), C(2)F(5), n-C(3)F(7), n-C(4)F(9)) have been prepared and characterized. The important physicochemical and electrochemical properties of these salts, including melting point, glass transition, viscosity, density, ionic conductivity, thermal and electrochemical stability, have been determined and comparatively studied with those based on the corresponding [BF(4)](-) and [(CF(3)SO(2))(2)N](-) salts. The influence of the structure variation in the quaternary ammonium cation and perfluoroalkyltrifluoroborate ([R(F)BF(3)](-)) anion on the above physicochemical properties is discussed. Most of these salts are liquids at 25 degrees C and exhibit low viscosities (58-210 cP at 25 degrees C) and moderate conductivities (1.1-3.8 mS cm(-1)). The electrochemical windows of these salts are much larger than those of the corresponding 1,3-dialkyimidazolium salts. Additionally, a number of [R(F)BF(3)](-) salts exhibit plastic crystal behavior.     

Spectroscopic properties of Nd3+ doped transparent oxyfluoride glass ceramics

In this paper, the spectroscopic properties of Nd(3+) doped transparent oxyfluoride glass ceramics containing LaF(3) nano-crystals were systematically studied. The formation and distribution of LaF(3) nano-crystals in the glass matrix were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Based on Judd-Ofelt theory, the intensity parameters Omega(t) (t=2, 4, 6), spontaneous emission probability, radiative lifetime, radiative quantum efficiency, width of the emission line and stimulated emission cross-section of Nd(3+) were evaluated. Particularly, the effect of Nd(3+) doping level on them was discussed. With the increase of Nd(3+) concentration in the glass ceramic, the experimental luminescence lifetime, radiative quantum efficiency and stimulated emission cross-section vary from 353.4 micros, 78.3% and 1.86 x 10(-20)cm(2) to 214.7 micros, 39.9% and 1.52 x 10(-20)cm(2), respectively. The comparative study of Nd(3+) spectroscopic parameters in different hosts suggests that the investigated glass ceramic system is potentially applicable as laser materials for 1.06 microm emission.     

Vibrational relaxation of methane by oxygen collisions: measurements of the near-resonant energy transfer between CH4 and O2 at low temperature

Vibrational relaxation in methane-oxygen mixtures has been investigated by means of a time-resolved pump-probe technique. Methane molecules are excited into selected rotational levels by tuning the pump laser to 2nu3 lines. The time evolution in population of various vibrational levels after the pumping pulse is monitored by probing, near 3000 cm-1, stretching transitions between various polyads like 2nu3(F2) - nu3, (nu3+2nu4) - 2nu4, and (nu3+nu4) - nu4 transitions. Measurements were performed from room temperature down to 190 K. A numerical kinetic model, taking into account the main collisional processes connecting energy levels up to 6000 cm(-1), has been developed to describe the vibrational relaxation. The model allows us to reproduce the observed signals and to determine rate coefficients of relaxation processes occurring upon CH4-O2 collisions. For the vibrational energy exchange, the rate coefficient of transfer from O2 (v = 1) to CH4 is found equal to (1.32 +/- 0.09) x 10(-12) cm3 molecule-1 s(-1) at 296 K and to (1.50 +/- 0.08) x 10(-12) cm3 molecule(-1) s(-1) at 193 K.     

A kinetic study of the reactions of Ca+ ions with O3, O2, N2, CO2 and H2O

The reactions between Ca(+)(4(2)S(1/2)) and O(3), O(2), N(2), CO(2) and H(2)O were studied using two techniques: the pulsed laser photo-dissociation at 193 nm of an organo-calcium vapour, followed by time-resolved laser-induced fluorescence spectroscopy of Ca(+) at 393.37 nm (Ca(+)(4(2)P(3/2)-4(2)S(1/2))); and the pulsed laser ablation at 532 nm of a calcite target in a fast flow tube, followed by mass spectrometric detection of Ca(+). The rate coefficient for the reaction with O(3) is essentially independent of temperature, k(189-312 K) = (3.9 +/- 1.2) x 10(-10) cm(3) molecule(-1) s(-1), and is about 35% of the Langevin capture frequency. One reason for this is that there is a lack of correlation between the reactant and product potential energy surfaces for near coplanar collisions. The recombination reactions of Ca(+) with O(2), CO(2) and H(2)O were found to be in the fall-off region over the experimental pressure range (1-80 Torr). The data were fitted by RRKM theory combined with quantum calculations on CaO(2)(+), Ca(+).CO(2) and Ca(+).H(2)O, yielding the following results with He as third body when extrapolated from 10(-3)-10(3) Torr and a temperature range of 100-1500 K. For Ca(+) + O(2): log(10)(k(rec,0)/cm(6) molecule(-2) s(-1)) = -26.16 - 1.113log(10)T- 0.056log(10)(2)T, k(rec,infinity) = 1.4 x 10(-10) cm(3) molecule(-1) s(-1), F(c) = 0.56. For Ca(+) + CO(2): log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -27.94 + 2.204log(10)T- 1.124log(10)(2)T, k(rec,infinity) = 3.5 x 10(-11) cm(3) molecule(-1) s(-1), F(c) = 0.60. For Ca(+) + H(2)O: log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -23.88 - 1.823log(10)T- 0.063log(10)(2)T, k(rec,infinity) = 7.3 x 10(-11)exp(830 J mol(-1)/RT) cm(3) molecule(-1) s(-1), F(c) = 0.50 (F(c) is the broadening factor). A classical trajectory analysis of the Ca(+) + CO(2) reaction is then used to investigate the small high pressure limiting rate coefficient, which is significantly below the Langevin capture frequency. Finally, the implications of these results for calcium chemistry in the mesosphere are discussed.     

High resolution quantum cascade laser studies of the ν3 band of methyl fluoride in solid para-hydrogen

Spectra of solid para-H(2) doped with CH(3)F at 1.8 K are studied in the ν(3) region (~1040 cm(-1)) using a quantum cascade laser source. As shown previously, residual ortho-H(2) in the sample (~1000 ppm) gives rise to distinct spectral features due to clusters of the form CH(3)F-(ortho-H(2))(N), with N = 0, 1, 2, 3, etc. Brief annealing at 7 K is found to give narrower spectral lines (≥0.006 cm(-1)) than conventional (5 K) annealing, and causes the N = 3 and 4 lines to fragment into two or more components. The N = 3 line is observed to be particularly stable and persistent. The N = 0 line (no ortho-H(2) neighbors) is resolved into two closely spaced (≈0.007 cm(-1)) components which are assigned to the K = 0 and 1 states of CH(3)F rotating around its C(3v) symmetry axis (ortho- and para-CH(3)F, respectively). Similar K-structure is also evident for other lines. Weak but persistent features ("N = 1/2 lines") are observed mid way between N = 0 and 1.     

Nano-graphite functionalized mesocellular carbon foam with enhanced intra-penetrating electrical percolation networks for high performance electrochemical energy storage electrode materials

Mesocellular carbon foam (MSU-F-C) is functionalized with hollow nanographite by a simple solution-phase method to enhance the intrapenetrating electrical percolation network. The electrical conductivity of the resulting material, denoted as MSU-F-C-G, is increased by a factor of 20.5 compared with the pristine MSU-F-C. Hollow graphite nanoparticles are well-dispersed in mesocellular carbon foam, as confirmed by transmission electron microscopy (TEM), and the d spacing of the (002) planes is 0.343 nm, which is only slightly larger than that of pure graphite (0.335 nm), suggesting a random combination of graphitic and turbostratic stacking. After nanographitic functionalization, the BET surface area and total pore volume decreased from 928 m(2) g(-1) and 1.5 cm(3) g(-1) to 394 m(2) g(-1) and 0.7 cm(3) g(-1), respectively. Thermogravimetric analysis in air shows that the thermal stability of MSU-F-C-G is improved relative to that of MSU-F-C, and the one-step weight loss indicates that the nanographite is homogeneously functionalized on the MSU-F-C particles. When the resulting mesocellular carbon materials are used as electrode materials for an electric double layer capacitor (EDLC), the specific capacitances (C(sp)) of the MSU-F-C and MSU-F-C-G electrodes at 4 mV s(-1) are 109 F g(-1) and 93 F g(-1), respectively. The MSU-F-C-G electrode exhibited a very high area capacitance (C(area), 23.5 μF cm(-2)) compared with that of the MSU-F-C electrode (11.7 μF cm(-2)), which is attributed to the enhanced intraparticle conductivity by the nanographitic functionalization. MSU-F-C-G exhibited high capacity retention (52%) at a very high scan rate of 512 mV s(-1), while only a 23% capacity retention at 512 mV s(-1) was observed in the case of the MSU-F-C electrode. When applied as an anode in a lithium ion battery, a significant increase in the initial efficiency (44%), high reversible discharge capacity (580 mA h g(-1)) in the lower voltage region, and a higher rate capability were observed. The high rate capability of the MSU-F-C-G electrode as charge storage was due to the low resistance derived from the nanographitic functionalization.     

Electronic spectroscopy of CoNe+ via mass-selected photodissociation

The CoNe(+) diatomic cation is produced by laser vaporization in a pulsed-nozzle source and studied with photodissociation spectroscopy at visible wavelengths. Vibronic structure is assigned to the (3)Π(2) ← (3)Δ(3) band system correlating to the Co(+)((3)P(2) ← (3)F(4)) + Ne asymptote. The origin band (13,529 cm(-1)) and a progression of 14 other vibrational bands are detected ending in the dissociation limit at 14,191 cm(-1). The excited state dissociation energy is therefore D(0)(') = 662 cm(-1), and an energetic cycle using this, the origin band energy, and the atomic transition produces a ground state dissociation energy of D(0)(") = 930 cm(-1). The excited state vibrational frequency is 116.1 cm(-1). A rotationally resolved study of the origin band confirms the electronic transition assignment and provides the bond distance of r(0)(") = 2.36 ?. The properties of CoNe(+) are compared to those of other CoRG(+) and MNe(+) complexes studied previously.     

Infrared laser spectroscopy of CH3...HF in helium nanodroplets: The exit-channel complex of the F + CH4 reaction

High-resolution infrared laser spectroscopy is used to study the CH3...HF and CD3...HF radical complexes, corresponding to the exit-channel complex in the F + CH4 --> HF + CH3 reaction. The complexes are formed in helium nanodroplets by sequential pickup of a methyl radical and a HF molecule. The rotationally resolved spectra presented here correspond to the fundamental v = 1 <-- 0 H-F vibrational band, the analysis of which reveals a complex with C(3v) symmetry. The vibrational band origin for the CH3...HF complex (3797.00 cm(-1)) is significantly redshifted from that of the HF monomer (3959.19 cm(-1)), consistent with the hydrogen-bonded structure predicted by theory [E. Ya. Misochko et al., J. Am. Chem. Soc. 117, 11997 (1995)] and suggested by previous matrix isolation experiments [M. E. Jacox, Chem. Phys. 42, 133 (1979)]. The permanent electric dipole moment of this complex is experimentally determined by Stark spectroscopy to be 2.4+/-0.3 D. The wide amplitude zero-point bending motion of this complex is revealed by the vibrational dependence of the A rotational constant. A sixfold reduction in the line broadening associated with the H-F vibrational mode is observed in going from CH3...HF to CD3...HF. The results suggest that fast relaxation in the former case results from near-resonant intermolecular vibration-vibration (V-V) energy transfer. Ab initio calculations are also reported (at the MP2 level) for the various stationary points on the F + CH4 surface, including geometry optimizations and vibrational frequency calculations for CH3...HF.     

Raman spectrum, quantum mechanical calculations and vibrational assignments of (95% alpha-TeO2/5% Sm2O3) glass

Chozen system of tellurite glasses doped with rare earth oxides (95% alpha-TeO(2)+5% Sm2O3) was prepared by melt quenching. Consequently, the Raman spectrum (150-1250 cm(-1)) of the modified tellurite have been recorded. As a continuation to our normal coordinate analysis, force constants and quantum mechanical (QM) calculations for tbp TeO4(4-) (triagonal bipyramid, C(2v)) and TeO(3+1); Te2O7(6-) (bridged tetrahedral), we have carried out ab initio frequency calculations for tpy TeO3(2-) (triagonal pyramidal, C(3v) and C(s)) and tp TeO3(2-) (triagonal planar, D(3h)) ions. The quantum mechanical calculations at the levels of RHF, B3LYP and MP2 allow confident vibrational assignments and structural identification in the binary oxide glass (95% alpha-TeO2 +5% Sm2O3). The dominant three-dimensional network structures in the modified glass are triagonal pyramidal TeO3 with minor features of short range distorted tbp TeO4 and bridged tetrahedral unit of TeO(3+1), leading to a structure of infinite chain. Therefore, alpha-TeO2/Sm2O3 (95/5%) glass experience structural changes from TeO4 (tbp); Te2O7 (TeO(3+1))-->TeO3 (tpy).     

Cooperative radiative and nonradiative effects in K2NaScF6 codoped with V3+ and Er3+

K2NaScF6 crystals codoped with V3+ and Er3+ exhibit some novel cooperative near-IR to visible upconversion processes at cryogenic temperatures. V3+ mainly acts as a broadband sensitizer. The V3+ 3T1g --> 3T2g excitation between 13,500 and 15,500 cm(-1), after fast relaxation to V3+ 1T2g, can be transferred to Er3+ 4I(11/2), and then upconversion takes place. Four upconversion mechanisms are identified and characterized. For narrow-band laser excitation the overall efficiency of the upconversion processes is low. However, at 12 K for broadband excitation, such as in a lamp, between 12,000 and 14,500 cm(-1) the number of emitted visible photons is roughly doubled by codoping V3+ in addition to Er3+.     

Green and red light emission by upconversion from the near-IR in Yb(3+) doped CsMnBr3

Direct near-IR excitation of Yb(3+) 2F(7/2)-->(2)F(5/2) levels at 10126, 10138, and 10596 cm(-1) in CsMnBr3:0.5%Yb(3+) leads to three types of luminescence at cryogenic temperatures: near-IR Yb(3+) emission and green and red upconverted luminescence. The green luminescence around 20 000 cm(-1) is identified as cooperative Yb(3+) pair upconversion. The broad red upconversion luminescence band centered at 14 700 cm(-1) is ascribed to the 4T(1g)-->6A(1g) transition of Mn(2+). Pulsed measurements indicate a sequence of ground-state absorption and excited-state absorption steps for the red upconversion process. One- and two-color excitation experiments support this, and we conclude that the red upconversion occurs by an exchange mechanism involving Yb(3+) and Mn(2+). The Yb(3+) 2F(5/2)-->(2)F(7/2) near-IR emission around 10 000 cm(-1) is also observed after Mn(2+) excitation at 21 838 cm(-1). This is indicative of a Mn(2+) 4T(1g)--> Yb(3+) 2F(5/2) relaxation process, which is a potential loss process for upconversion efficiency.     

The spectroscopic properties of Er(3+)-doped TeO(2)-Nb(2)O(5) glasses with high mechanical strength performance

(100-x)TeO(2)-xNb(2)O(5) (x=5-20) niobic tellurite glasses doped with 0.5 mol.% Er(2)O(3) were synthesized, and their thermal, mechanical, and spectroscopic properties were measured and compared to the properties of the typical 75TeO(2)-20ZnO-5Na(2)O (TZN) tellurite glass. The refractive index (n(d)), density (rho), and glass transition temperature (T(g)) of bulk glasses increase with the Nb(2)O(5) content. The Vickers microhardness (H(v)) of bulk glass in niobic tellurite glasses also increases with the Nb(2)O(5) content. The values (2.5-3.2GPa) of H(v) in the niobic tellurite glasses are 47-88% larger than that (1.7GPa) in TZN glass. The effect of Nb(2)O(5) content on absorption spectra, the Judd-Ofelt parameters Omega(t) (t=2, 4, 6), fluorescence spectra and the lifetimes of Er(3+):I(13/2) level were also investigated, and the stimulated emission cross-section was calculated from McCumber theory. With increasing Nb(2)O(5) content in the glass composition, the Omega(t) (t=2, 4, 6) parameters, fluorescence full width at half maximum (FWHM) of I(13/2) of Er(3+) increase, while the (4)I(13/2) lifetimes of Er(3+) decreases. Compared with TZN glass, the gain bandwidth properties of Er(3+)-doped TeO(2)-Nb(2)O(5) glass is much larger than in tellurite glass based TeO(2)-ZnO-Na(2)O system, bismush-based glass, germanate, and silicate glasses, which indicates that TeO(2)-Nb(2)O(5) glasses are better choice as a practical available host material for broadband Er(3+)-doped amplifier.     

Analysis of energy level structure and excited-state dynamics in a Sm 3+ complex with soft-donor ligands: Sm(Et2Dtc)3(bipy)

Using both laser-excited fluorescence and optical absorption methods, we have determined 57 crystal-field (CF) energy levels of Sm 3+ in crystals of Sm(Et2Dtc)3(bipy). The analysis of the energy levels is based on a model Hamiltonian consisting of both free-ion and CF terms. The CF modeling of the experimental energy levels yielded physically reasonable Hamiltonian parameters with a final rms deviation of 17.3 cm(-1). In comparison with Sm 3+ in other hosts, the CF splitting of Sm 3+ in the lattice of Sm(Et2Dtc)3(bipy) is rather weak. The observed fluorescence decay of the 4G(5/2) manifold is single-exponential, with a lifetime of 24.5 mus, indicating only one site of Sm3+ in the lattice. According to the Judd-Ofelt theory, values of three intensity parameters were obtained (Omega(2,4,6) = 1.57, 2.65, and 3.65, in units of 10(-20) cm(-1)). The calculated branching ratios for transitions from the 4G(5/2) manifold are in agreement with experimental values. The calculated radiative lifetime of the 4G(5/2) manifold is 3.24 ms, and the corresponding fluorescence quantum efficiency is only 0.75%. Efficient multiphonon relaxation processes induced by the localized high-frequency vibrational modes in the bipyridyl group may lead to the extremely low quantum efficiency observed. The thermal line broadening and shifts of the 4G(5/2)(1) --> 6F(1/2) transition were observed and fitted very well by the McCumber-Sturge equations with an assumption of Raman phonon scattering processes as the leading relaxation mechanism. The Debye temperature for this crystal is predicted to be 350 K.     

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

Relaxation of highly vibrationally excited pyrimidine (C(4)N(2)H(4)) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E(')=40 635 cm(-1)) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 00(0)0 ground state of CO(2) resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO(2) recoil velocity distribution for J=58-80 of the 00(0)0 state. Rate constants and probabilities for collisions populating these CO(2) rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of DeltaE to create the energy transfer distribution function, P(E,E(')), from E(')-E approximately 1300-7000 cm(-1). P(E,E(')) is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO(2) and parameters that can be compared to previously studied systems using this technique, pyrazineCO(2), C(6)F(6)CO(2), and methylpyrazineCO(2). P(E,E(')) parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E(')) is analyzed in the context of two models, one which suggests that the shape of P(E,E(')) is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E(')) can be determined by how the donor molecule final density of states changes with DeltaE.     

Vibrational relaxation of O2(X3 Sigma g-, v = 9-13) by collisions with O2

Vibrationally excited O(2)(X(3) Sigmag(-)) was generated in the UV laser flash photolysis of O(3) and single vibrational level was detected via laser-induced fluorescence (LIF) in the B(3) Sigmau(-)-X(3) Sigmag(-) system. The time-resolved LIF of adjacent vibrational levels has been analyzed by the integrated-profiles method and the rate coefficients for single-quantum relaxation, O(2)(X(3)Sigmag(-), v = 9-13)+ O(2)(v = 0)--> O(2)(X(3)Sigmag(-), v - 1)+ O(2)(v = 1), have been determined. To the best of our knowledge, the rate coefficients for v = 12 and 13 are measured for the first time in the present study. The efficiency of relaxation is higher at lower vibrational levels, indicating that a small energy mismatch is suitable for the energy transfer. The vibrational level dependence of all the rate coefficients for the relaxation measured in the present study and previously reported by several groups can be rationalized by the energy gap law.