N2- and O2-broadening of CO2 for the (301)III ← (000) band at 6231 cm

The N₂- and O₂-broadening effect have been investigated for 10 absorption lines of the CO₂ (30⁰1)_III ← (00⁰0) band centered at 6231 cm⁻¹, in the range from P(28) to R(28) by a near-infrared diode-laser spectrometer. We have analyzed the observed line profiles with the Galatry function, and determined the N₂- and O₂-broadening coefficients precisely. The air-broadening coefficients for these lines have been derived. The present results are compared with those of the previous studies for this band and with some of the other bands.     

Spectral line parameters in the (3 ← 0) overtone band of the HI molecule and line-mixing in the band head

The linestrengths, self-pressure broadening and shifting coefficients have been measured for P₃ (10)- R₃ (12) lines in the second overtone band of hydrogen iodide. A dipole moment function in terms of the reduced nuclear displacement x = (R − R_e)/R_e is obtained using rotationless dipole matrix elements determined by the Herman-Wallis analysis of the (1, 2, 3 ← 0) HI bands: μ (x) = 0.4471(5) − 0.0770(2)x + 0.547(3)x² − 1.93(2)x³, in a full agreement with the function proposed previously [J. Mol. Spectrosc. 223 (2004) 67]. A close match is demonstrated of the results of most recent relativistic calculations [Phys. Chem. Chem. Phys. 6 (2004) 3779] with the spectroscopically derived electric dipole parameters for HI. Line-mixing in the band head is observed, the self-pressure shifting and broadening coefficients for the (3 ← 0) band lines are determined.     

Multispectrum analysis of the ν4 band of CH3CN: Positions, intensities, self- and N2-broadening, and pressure-induced shifts

A multispectrum nonlinear least-squares fitting technique was applied to measure accurate zero-pressure line center positions, Lorentz self- and nitrogen (N₂)-broadened half-width coefficients, and self- and N₂-pressure-induced shift coefficients for over 700 transitions in the parallel ν₄ band of CH₃CN near 920 cm⁻¹. Fifteen high-resolution (0.0016 cm⁻¹) laboratory absorption spectra of pure and N₂-broadened CH₃CN recorded at room temperature using the Bruker IFS 125HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL) in Richland, Washington, USA, were analyzed simultaneously assuming standard Voigt line shapes. Short spectral intervals containing manifolds of transitions from the same value of J were fitted together. In all, high-precision line parameters were obtained for P(44)-P(3) and R(0)-R(46) manifolds. As part of the analysis, quantum assignments were extended, and the total internal partition function sum was calculated for four isotopologs: ¹²CH₃¹²CN, ¹³CH₃¹²CN, ¹²CH₃¹³CN, and ¹³CH₃¹³CN. Measurements of N₂ broadening, self-broadening, N₂-shift, and self-shift coefficients for transitions with J up to 48 and K up to 12 were measured for the first time in the mid-infrared. Self-broadened half-width coefficients were found to be very large (up to ∼2 cm⁻¹ atm⁻¹ at 296 K). Ratios of self-broadened half-width coefficients to N₂-broadened half-width coefficients show a compact distribution with rotational quantum number in both the P and R branches that range from ∼4.5 to 14 with maxima near ∣m∣=24, where m=−J″, J″, and J″+1 for P, Q, and R lines, respectively. Pressure-induced shifts for N₂ are small (few exceed ±0.006 cm⁻¹ atm⁻¹ at 294 K) and are both positive and negative. In contrast, self-shift coefficients are large (maxima of about ±0.08 cm⁻¹ atm⁻¹ at 294 K) and are both positive and negative as a function of rotational quantum numbers. The present measured half-widths and pressure shifts in ν₄ were compared with corresponding measurements of rotational transitions.     

Current conduction mechanism in Al/p-Si Schottky barrier diodes with native insulator layer at low temperatures

The forward bias current-voltage (I-V) characteristics of Al/p-Si (MS) Schottky diodes with native insulator layer were measured in the temperature range of 80-300 K. The obtained zero bias barrier height Φ_B0(I-V), ideality factor (n) and series resistance (R_s) determined by using thermionic emission (TE) mechanism show strong temperature dependence. There is a linear correlation between the Φ_B0(I-V) and n because of the inhomogeneties in the barrier heights (BHs). Calculated values from temperature dependent I-V data reveal an unusual behaviour such that the Φ_B0 decreases, as the n and R_s values are increasing with decreasing absolute temperature, and these changes are more pronounced especially at low temperatures. Such temperature dependence of BH is contradictory with the reported negative temperature coefficient of the barrier height. In order to explain this behaviour we have reported a modification in the expression reverse saturation current I_o including the n and the tunnelling factor (αΧ^1/2δ) estimated to be 15.5. Therefore, corrected effective barrier height Φ_bef.(I-V) versus temperature has a negative temperature coefficients (α = −2.66 × 10⁻⁴ eV/K) and it is in good agreement with negative temperature coefficients (α = −4.73 × 10⁻⁴ eV/K) of Si band gap. In addition, the temperature dependent energy distribution of interface states density N_ss profiles was obtained from the forward bias I-V measurements by taking into account the bias dependence of the Φ_e and n. The forward bias I-V characteristics confirm that the distribution of N_ss, R_s and interfacial insulator layer are important parameters that the current conduction mechanism of MS Schottky diodes.     

Low and room temperature measurements and calculations of O2-broadening coefficients in the ν3 band of CS2

O₂-broadening coefficients have been measured for 16 lines in the P and R branches of the fundamental ν₃ band of ¹²C³²S₂ at room and low temperatures (298.0, 273.2, 248.2, 223.2, and 198.2 K), using a tunable diode laser spectrometer and a low temperature cell. These lines from P(62) and R(64) are located in the spectral range 1519-1547 cm⁻¹. The collisional half-widths are obtained by fitting each observed profile with the Voigt and Rautian lineshape models. The broadening coefficients have also been calculated at all experimental temperatures using a semiclassical calculation performed by considering in addition to the electrostatic quadrupole-quadrupole interaction, a simple anisotropic contribution. Finally, from all the results, the parameter n of the temperature dependence of the broadening coefficients has been determined both experimentally and theoretically.     

Doppler-limited spectroscopy of the AΠ1 ← XΣ system of ICl in the 0.8 μm region using a Ti:sapphire ring laser

Doppler-limited vib-rotational absorption spectra of the A ← X electronic transition of I^35/37Cl are measured in the range 11,352-13,507 cm⁻¹ using a Ti:sapphire ring laser. The P-, Q-, and R-branch lines belonging to the v ← v″ = (0-7) ← (0-7) transition in I³⁵Cl and the v ← v″ = (0-6) ← (2-6) transition in I³⁷Cl are assigned. Under Doppler-limited conditions, the P- and R-branch lines are split into doublets by the nuclear quadrupole coupling effect of the I atom. The unperturbed positions of these lines are correctly calculated, whereas splitting in the Q-branch lines was not observed. The mass-reduced Dunham expansion coefficients U_l,m of the A and X states and the spectroscopic constants , and H_v^′ of the A state are determined using a global least-squares fitting procedure.     

Intensity measurements in the 2v3-band of 13CH4 at low temperatures

Absolute intensities of the J-multiplets P(1)-P(8), R(0)-R(7) and of the Q-branch in the 2v₃-band of ¹³CH₄ have been measured at 100, 150, 200, and 296°K. Our intensity data confirm the recent observation by Fox et al. that substitution of the isotope ¹³C for the central ¹²C atom in methane results in significantly different line strengths in the severely perturbed 2v₃-band. Our results at 296°K for the absolute intensities of R(0) and R(1) are in excellent agreement with the values measured by Fox et al.     

Self-broadening coefficients and absolute line intensities in the ν4 + ν5 band of acetylene

Self-broadening coefficients and line strengths have been measured at room temperature for 30 lines of C₂H₂ in the P and R branches of the ν₄ + ν₅ band, using a tunable diode laser spectrometer. These lines, ranging from P(22) to R(23), are located in the spectral range 1275-1390 cm⁻¹. A semiclassical calculation of the line broadenings has been performed considering the main electrostatic interactions and an anisotropic dispersion contribution leading to results in satisfactory agreement with the experimental data.     

Diode laser spectroscopy of the ν9 band of ethyl chloride

The vibration-rotation spectrum of the ν₉ band of C₂H₅Cl was recorded using a Nicolet 7199 Fourier Transform Infrared Spectrometer; the Q-branch, R(5)-R(6) multiplets, and P(21)-P(22) multiplets were investigated using a tunable semiconductor diode laser spectrometer. Constants derived from these assignments are (cm^?1) ν₉ = 973.8379(2), A⁹ = 1.039516(3), B⁹ = 0.183081(7), C⁹ = 0.164505(8). The line which coincides with the CO₂ laser 10R(6), which has been employed in multiphoton dissociation studies, is tentatively assigned to the 20_{3 18}-21_{3 19} transition. In addition, a very strong coincidence of transitions 19_{9 11}-19_{9 10} and 19_{9 10}-19_{9 11} with the CO₂ 10R(16) line is found, which can provide a good candidate for laser chemistry and infrared double resonance spectroscopy.     

Absolute Position of the D′2g(P2) Ion-Pair State of I2 Determined by Perturbation-Facilitated Optical-Optical Double Resonance

We have reexamined the sequential two-photon absorption of I₂ from the X¹Σ_g⁺ ground state to the lowest D′2_g(³P₂) ion-pair state using the high vibrational level of the B³Π(0_u⁺) state as an intermediate. The double resonance transition to the D′2_g(³P₂) state was found to occur through the B³Π(0_u⁺)-b′2_u coupled state by hyperfine interaction, which permits to mix the different J levels of different electronic states. We elucidated the B³Π(0_u⁺)-b′2_u coupling schemes in the intermediate states. The double resonance spectra recorded for the D′2_g(³P₂) state in the range v=0-30 were used to determine the absolute energy of the D′2_g(³P₂) state. The molecular parameters of the D′2_g(³P₂) state obtained in this study are Y₀₀=40 388.783(2), Y₁₀=103.956 46(57), Y₂₀=−0.207 717(51), Y₃₀=2.199(13)×10⁻⁴, Y₀₁=0.020 528 18(62), and Y₁₁=−5.1753(48)×10⁻⁵ (all in cm⁻¹ and σ in parentheses). An RKR potential curve constructed using these constants is reported. Combined with the data on the D′2_g(³P₂)-A′³Π(2_u) transition from Zheng et al. (J. Chem. Phys.96, 4877 (1992)), we can locate the A′³Π(2_u) v=0 state at 10 096.444(6) cm⁻¹ above the ground state.     

The Electronic Transition Moment Function for the BΠ-XΔ System of TiO

Several vibronic bands associated with v′=0, 1, and 2 for the B³Π-X³Δ transition of TiO have been observed using a dispersed laser induced fluorescence (DLIF) technique. From intensity distributions of the DLIF spectra, the dependence of the electronic transition moment R_e(r) for the B³Π-X³Δ system was determined as a function of the internuclear distance r. For the determination of the R_e(r) function, a merged fit of the observed distributions, the reported radiative lifetimes of three vibrational levels in the B³Π state, and the reported value of R_e(r) for the (0, 0) band were performed; R_e(r) was determined as R_e(r)=1.3723(79)[1−0.316(81)(r−r₀)+2.0(10)(r−r₀)²](r₀=1.6648 Å and 1.5131 Å≤r≤1.8636 Å). The r-dependence of R_e(r) was much smaller than the reported theoretical predictions. The obtained values of R_e(r) were analyzed simultaneously with the hyperfine coupling constants for the X³Δ state and the spin-orbit constants for the X³Δ and B³Π states to assess the ionic and orbital characters. It was found that the r-dependence of R_e(r) could be accounted for by both the configuration interaction in the B³Π state and the polarization in the unpaired 9σ and 4π orbitals.     

ρ-ω mixing in J/ø→VP decays

The study of ρ-ω mixing has mainly focused on vector meson decays with isospin I=1, namely the ρ(ω)→π⁺π^- process. In this paper, we present a study of ρ-ω mixing in ρ(ω)→π⁺π^-π⁰ (I=0) using a flavor parameterization model for the J/ø→ VP process. By fitting a theoretical framework to PDG data, we obtain the SU(3)-breaking effect parameters s_V=0.03±0.12, s_P=0.17±0.17 and the ρ-ω mixing polarization operator ∏_ρω=(0.006±0.011) GeV². New values are found for the branching ratios when the mixing effect is incorporated: Br(J/ψ→ ωπ⁰) = (3.64 ±0.37)×10^-4, Br(J/ψ→ ωη) = (1.48 ±0.17)×10^-3, Br(J/ψ→ ωη') = (1.55±0.56)×10^-4, these are different from the corresponding PDG2012 values by 19%, 15% and 15%, respectively.     

Theoretical absolute J-manifold intensities of the ν3 fundamental of GeH4

Theoretical absolute integrated of the J-manifolds P(1)-P(20), R(0)-R(20), and the central Q-branch in the ν₃ fundamental of GeH₄ have been projected from experimental intensity measurements. Values are presented in tabular form as a function of temperature from 200 to 340°K in 20°K increments.     

Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Transition Probabilities in the BΣ-XΣ and the BΣ-AΠ Electronic Systems of MgO

Transition probabilities for the B¹Σ⁺-X¹Σ⁺ and the B¹Σ⁺-A¹Π electronic systems are presented for v=0-4 and J=0-150 in each electronic state. The functional form of the electronic transition moment for the B-X transition is taken from published ab initio results. The B-A moment is assumed to have the same form and is scaled using empirical branching ratio data. The R_e(r) are used with Rydberg-Klein-Rees (RKR) wavefunctions to calculate transition probabilities for v=0-4 and J=0-150. The RKR potentials were calculated based on empirical spectroscopic constants.     

Absolute intensities and pressure broadening coefficients measured at different temperatures for the 201II ← 000 band of 12C16O2 at 4978cm-1

Absolute line intensities and self-broadening coefficients have been measured at 197° and 294°K for the 201_II ← 000 band of ¹²C¹⁶O₂ at about 4978cm^-1. The vibration-rotation factor (F_VR), the purely vibrational transition moment (∣R(O)∣), and the integrated band intensity (S_band) are deduced from the measurements. The results are: F_VR(m)=1+(0.24±0.08)x10^-4m+(0.55+0.21)x10^-4m², ∣R(O)∣= (4.340±0.008x10^-3 debye, S_band=96372±190cm^-1km^-1atm^-1_STP. The results for self-broadening coefficients, as well as for individual vibration-rotation lines, are presented in the text.     

N2-broadening coefficients in the ν2 and ν4 bands of PH3

N₂-broadening coefficients are measured for 61 transitions of PH₃ in the ^QR branch of the ν₂ band and the ^PP, ^RP, ^SP, and ^PQ branches of the ν₄ band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 1 to 16 and K from 0 to 11 are located between 1008 and 1106 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter models provide larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the electrostatic contributions. The theoretical results are in good agreement with the experimental data and reproduce the J dependence of the broadenings, but their decrease at high J values is overestimated for the ^QR (J, K) transitions.     

Hydrogen line broadening in the ν2 and ν4 bands of phosphine at low temperature

Using a tunable diode-laser spectrometer, we have measured H₂-broadening coefficients of PH₃ at low temperature (173.2 K) for 27 lines in the ^QR branch of the ν₂ band and in the ^PP and ^RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 11 and K from 0 to 9 are located between 1016 and 1093 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile and a speed-dependent Rautian profile which provides slightly larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the weak electrostatic contributions. Except for three ^QR(J,K) lines, where K = J, the calculated broadening coefficients are in good agreement with the experimental data. By comparing the results obtained at room and low temperatures, the temperature dependence of linewidths has been determined both theoretically and experimentally.     

The electro-optic kerr effect in noncentrosymmetric KH2PO4 and KD2PO4 monocrystals

Experimental and theoretical results of the determination of the quadratic electro-optic coefficients in noncentrosymmetric KH₂PO₄(KDP) and KD₂PO₄(DKDP) monocrystals are presented. The coefficientR _c=R ₁₁₂₂-R ₁₁₁₁ for the X-cut crystals has been measured by a dynamic method in the a.c. electric field. The theoretical value of the coefficient has been calculated by the Kurtz-Robinson model. It has been found that the coefficientR _c was less than 10×10^–20m²V^–2.     

Broadening, shifting, and line mixing in the 030 ← 010 parallel Q branch of N2O

The 03¹0 ← 01¹0 parallel Q branch of N₂O has been studied at 297 K and over the pressure range 1-130 torr. Absorption spectra were recorded using a high resolution (1.5 MHz or 5 × 10⁻⁵ cm⁻¹) and high signal-to-noise (>3500:1) mid-infrared spectrometer based on difference-frequency infrared generation in AgGaS₂. In the low-pressure range (1-11 torr) we obtained accurate values for the line strengths, the broadening coefficients, the weak mixing coefficients, and the overall shifting of the branch. The medium pressure results, ranging from 23 to 130 torr, were analyzed by treating the band as a whole, using a relaxation matrix formalism, based on an energy gap scaling law. We find, effectively, that only 36% of the rotationally inelastic collisions are associated with Q branch mixing, the rest presumably being associated with Q-P and Q-R mixing in the same vibrational band. The pressure shifting coefficient of the 03¹0 ← 01¹0 Q branch as a whole was also determined and found to be 5.8 × 10⁻³ cm⁻¹/atm towards lower frequencies.