Frequency measurement of pure rotational transitions in the v2 = 1 state of H2O

Frequencies of pure rotational transitions in the v₂ = 1 vibrationally excited state of H₂¹⁶O were measured with a tunable far-infrared spectrometer in the frequency range of 0.5-5 THz. Molecular parameters of Watson’s A-reduced Hamiltonian have been obtained to reproduce the observed frequencies.     

Measurements of positions, strengths and self-broadened widths of H2O from 2900 to 8000 cm: line strength analysis of the 2nd triad bands

High-resolution spectra of H₂O were recorded with a Fourier-transform spectrometer covering H₂O transitions from 2900 to 8000 cm⁻¹. Over 13,000 absorptions were measured to determine line positions, strengths and self-broadened half-width coefficients. The H₂ ¹⁶O line strengths of the (0 3 0)-(0 1 0), (1 1 0)-(0 1 0), (0 1 1)-(0 1 0) and (0 3 0)-(0 0 0), (1 1 0)-(0 0 0), (0 1 1)-(0 0 0) bands were fitted to a quantum mechanical model which involves the interactions between the (0 3 0), (1 1 0), and (0 1 1) vibrational states. Also fitted were experimental strengths of the hot bands; (1 2 0)-(0 1 0) and (0 2 1)-(0 1 0). The model includes 14 dipole matrix elements for B- and A-type transitions. The measured line positions were used along with hot water emission measurements (for the (0 3 0), (0 4 0), and (0 5 0) states of H₂ ¹⁶O) in an analysis to obtain high-accuracy energy level values in the (0 3 0), (1 1 0), (0 1 1), (0 4 0), (1 2 0), (0 2 1), (2 0 0), (1 0 1), (0 0 2), and (0 5 0) vibrational states of H₂ ¹⁶O and the (1 1 0) and (0 1 1) states of H₂ ¹⁷O. Also included were measurements and analysis of self-broadened half-widths for over 4700 absorptions between 4405 and 7729 cm⁻¹. The results from this investigation provide new information for the noted H₂ ¹⁷O bands and present a more accurate representation of the measured H₂ ¹⁶O bands.     

Line shift and mixing in the ν4 and 2ν2 band of NH3 perturbed by H2 and Ar

Pressure induced line shift and line mixing parameters have been measured for 66 rovibrational lines in the ν₄ band and for 10 lines in the 2ν₂ band of NH₃ perturbed by H₂ and Ar at room temperature (T = 296 K). These lines with J values ranging from 2 to 10 are located in the spectral range 1450-1600 cm⁻¹. Experiments were made with a high-resolution Fourier transform spectrometer. The line shifts and line mixing parameters have been derived from the non-linear least-square multi-pressure fitting technique. The shift coefficients are compared with those calculated from the Robert-Bonamy formalism (RB). The results are generally in satisfactory agreement with the experimental data.     

Collisional broadening and line intensities in the ν2 and ν4 bands of PH3

Using a tunable diode-laser spectrometer self-broadening coefficients and absolute intensities have been measured for 26 lines of PH₃ at 298 K in the QR branch of the ν₂ band and the PP and RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 14 and K from 0 to 11 are located in the spectral range 995-1093 cm⁻¹. Self-broadening coefficients have also been measured at 173.4 K for nine of these lines. The collisional widths and line strengths are obtained by fitting each spectral line with different theoretical profiles. The results obtained for the line intensities are in good agreement with recent measurements [J. Mol. Spectrosc. 215 (2002) 178]. The self-broadening coefficients are also calculated on the basis of a simple semiclassical model involving only the electrostatic interactions. A satisfactory agreement is obtained except for high J values or K values equal to J, for which the calculated results are notably underestimated. By comparing broadening coefficients at room and low temperatures, the temperature dependence of these broadenings has been determined both experimentally and theoretically.     

The Raman spectra and cross-sections of the ν2 band of H2O, D2O, and HDO

We report the experimental Raman spectra of the ν₂ band of H₂O, D₂O, and HDO in the vapor phase at room temperature. A complete interpretation of the Raman intensities is carried out employing the variational rovibrational wavefunctions obtained from a Hamiltonian in Radau coordinates and an ab initio polarizability surface at 514.5 nm. We show the importance of the rotation-vibration coupling to obtain the correct line intensities. Several tables with the assignments of the individual rotational-vibrational transitions and their Raman scattering strengths are reported. From these tables, the ν₂ Raman spectra can be simulated up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Mechanism of amorphous Ge2Sb2Te5 removal during chemical mechanical planarization in acidic H2O2 slurry

In this paper, chemical mechanical planarization (CMP) of amorphous Ge2Sb2Te5 (a-GST) in acidic H2O2 slurry is investigated. It was found that the removal rate of a-GST is strongly dependent on H2O2 concentration and gradually increases with the increase in H2O2 concentration, but the static etch rate first increases and then slowly decreases with the increase in H2O2 concentration. To understand the chemical reaction behavior of H2O2 on the a-GST surface, the potentiodynamic polarization curve, surface morphology and cross-section of a-GST immersed in acidic slurry are measured and the results reveal that a-GST exhibits a from active to passive behavior for from low to high concentration of H2O2 . Finally, a possible removal mechanism of a-GST in different concentrations of H2O2 in the acidic slurry is described.     

High-resolution FTIR measurement of the ν4 band of methylene fluoride-d2

A high-resolution (0.002 cm⁻¹) infrared absorption spectrum of methylene fluoride-d₂ (CD₂F₂) of the lowest fundamental mode ν₄ in the region from 460 to 610 cm⁻¹ has been measured on a Bruker IFS 120-HR Fourier transform infrared spectrometer. More than 3500 transitions have been assigned in this B-type band centered at 521.9 cm⁻¹. The data have been combined with upper state pure rotational measurements in a weighted least-squares fit to obtain molecular constants for the upper state resulting in an overall standard deviation of 0.00018 cm⁻¹. Accurate value for the band origin (521.9578036 cm⁻¹) has been obtained and inclusion of transitions with very high J (?60) and K_a (?34) values has resulted in improved precision for sextic centrifugal distortion constants, in particular D_K, H_KJ, and H_K.     

High-resolution study of some doubly excited vibrational states of PH2D: the ν1+ν2, ν2+ν5, ν2+ν3, and ν2+ν6 bands

The absorption bands ν₁+ν₂, ν₂+ν₃, and ν₂+ν₆ of PH₂D have been recorded for the first time using a high-resolution Bruker 120 HR interferometer, and rotationally analyzed. Some transitions belonging to the very weak band ν₂+ν₅ and enhanced in intensity by strong interactions with the ν₁+ν₂ band were also assigned. Sets of parameters obtained from the fit reproduce experimental line position of the bands ν₁+ν₂ and ν₂+ν₃ with about the experimental accuracy. The residuals of the ro-vibrational energies of the ν₂+ν₆ band are about 10 times larger. Reasons for the poorer reproduction of the latter data are given.     

Atomic-potential parameters for H2 and D2: quantum corrections in the calculation of second-virial coefficients

First-order quantum corrections were introduced into the computation of the second-virial coefficients of H₂ and D₂. The quantum effects, for the studied two light molecules, are considerable even at the room temperature and become prominent at low temperatures. Atomic potentials, incorporating the quadrupole interactions, were employed in the calculations. Optimum atomic-potential parameters ε_H, σ_H, ε_D and σ_D were obtained from the nonlinear least-squares fit of the experimental second-virial coefficients. The fitted virial coefficients cover the temperature ranges of 173-423 and 153- for H₂ and D₂, respectively.     

Air-broadening coefficients of the HO2 radical in the 2ν1 band measured using cw-CRDS

In this paper we present measurements of the air-broadening coefficients of HO₂ at room temperature in the 2ν₁ band around 1.5 microns. The HO₂ radicals were created by flash photolysis of SOCl₂ in a flow of O₂/CH₃OH mixtures. To observe air-broadening, N₂ (79%) and O₂ (21%) were added using calibrated flow controllers and a total pressure controller. The total pressure was monitored in parallel using a capacitive pressure gauge. Air-broadening coefficients at 296 K were determined for 34 absorption lines between 6631 and 6671 cm⁻¹. The air-broadening coefficients of HO₂ show a rotational dependence (decreasing from about 0.14 cm⁻¹/atm for N″ = 3 to about 0.09 cm⁻¹/atm for N″ = 10). No evidence for collisional narrowing was observed.     

External cavity tunable diode laser spectra of the ν1 + 2ν4 stretch-bend combination bands of NH3 and NH3

The ammonia ν₁ + 2ν₄ perpendicular stretch-bend combination band has been investigated in spectra of ¹⁴NH₃ and ¹⁵NH₃ recorded in the 6400-6800 cm⁻¹ region with an external cavity tunable diode laser (ECTDL) spectrometer. For ¹⁴NH₃, new assignments were determined initially by extrapolating from published low-J jet-cooled beam results up to transitions of higher J and K. Corresponding ν₁ + 2ν₄ transitions for the ¹⁵NH₃ species were then found by identifying similar patterns of lines with a characteristic downshift of approximately 9.7 cm⁻¹. Assignments were confirmed employing ground-state combination differences. Term values, a-s inversion splittings, l-doubling energies and parameter estimates from simple single-state fits are reported for the two ammonia species.     

High-resolution FTIR spectroscopy of the 3ν2 band of PH3

High-resolution Fourier transform spectrum of phosphine (PH₃) at room temperature has been recorded in the region of the 3ν₂ band (2730-3100 cm⁻¹) at an apodized resolution of 0.005 cm⁻¹. About 200 vibration-rotation transitions have been least squares fitted with an rms of 0.00039 cm⁻¹ after taking into account the ΔK = ±3 interaction.     

基于微型多次反射腔的TDLAS二氧化碳测量系统

海气界面CO₂测量对于海洋科学研究具有重要意义,在目前的海洋CO₂测量仪器中,基于可调谐二极管激光吸收光谱技术(TDLAS)的设备因灵敏度高、环境适应性强等特点受到关注。TDLAS系统的体积和灵敏度通常受限于多次反射腔的大小和光程。针对海洋CO₂脱气量小且灵敏度高的测量需求,自主设计了一套微型多次反射腔,用于TDLAS系统的CO₂测量。该微型多次反射腔采用两片口径为25.4 mm、焦距为50 mm的球面反射镜,以38 mm的腔长实现了253次反射,获得了约10 m的光程,封装后的样品池体积仅有90 mL。基于该微型多次反射腔搭建了一套直接吸收TDLAS的CO₂气体浓度测量系统,通过标准气体对该系统进行了测试,检测限约为26×10-6,不同浓度气体线性相关度R2为99.986%。同时还将该系统与LGR公司生产的便携式温室气体分析仪(UGGA)进行了对比测量,结果表明二者在白天CO₂浓度波动较大和夜晚CO₂浓度变化较平稳两种情况下均表现出较好的一致性,R2大于97%。实验结果证明了系统性能,下一步将优化试验装置并进行现场应用。     

Controlled synthesis of BaWO4 hierarchical nanostructures by exploiting oriented attachment in the solution of H2O and C2H5OH

Shape-controlled synthesis of BaWO₄ hierarchical nanostructures has been successfully achieved by exploiting oriented attachment in a mixture of water and ethanol. A controlled change in the volume ratio of C₂H₅OH and H₂O or the concentration of initial reagents has resulted in the synthesis of products of various morphologies, such as shuttle-like, ellipsoid-like, and flower-like ones. The obtained products are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. The altered nucleation and growth rates of primary particles that assembled to the final hierarchical nanostructures through oriented attachment are the main cause of the evolution of their morphologies. The room-temperature photoluminescent intensities of the products strongly depend on their morphology.     

Observation of hot bands in the infrared spectrum of H2CO

Two hot bands in the infrared spectrum of formaldehyde (H₂CO) have been identified by means of tunable infrared laser spectroscopy using a jet-cooled sample. One band falls in the region 2760-2800 cm⁻¹; it follows a-type selection rules and it has been assigned as the ν₁ + ν₄ − ν₄ hot band. The other band falls in the region 2800-2860 cm⁻¹; it follows b-type selection rules and it has been assigned as the ν₅ + ν₄ − ν₄ hot band. The observations are restricted to low J and K_a levels. It has consequently been possible to ignore the effects of the extensive Coriolis couplings involving these levels in the analysis of the spectra and to model the rotational structure as that of a simple asymmetric top. Least-squares fits of the data have provided values for the band origins: 2774.2706(11) cm⁻¹ for the ν₁ + ν₄ − ν₄ and 2829.2621(8) cm⁻¹ for the ν₅ + ν₄ − ν₄ band. Term values for the upper vibrational levels involved in the transitions have been determined by use of the previously reported term values for the v₄ = 1 level.     

Line shape of the far-wing beyond the band head of the CO2ν3 band

Carbon dioxide is one of the most important trace gases in the terrestrial atmosphere. The spectral data required in remote sensing are the spectral parameter of each absorption line and a line shape model. This paper describes the absorption properties of CO₂ near 2400 cm⁻¹; these properties are of interest to those in the atmospheric temperature sounding field. The shape of the far-wing of N₂- and O₂-broadened CO₂ lines was investigated in the 2200-2500 cm⁻¹ spectral region in a temperature range of atmospheric interest (230-318 K). We focused on the higher rotational quantum number of the R-branch in the ν₃ band, where the effect of the far-wing is enhanced. The effect of the far-wing has been studied extensively by others, since the CO₂ν₃ band is known to exhibit sub-Lorentzian behavior. Here, we show the observed spectra along with calculated spectra for five temperatures. We used first-order line-mixing and the χ-factor, which accounts for the effect of the far-wing, to create the calculated spectra. Our results provide new knowledge of quantum interference of the spectral line in the ν₃ band of CO₂.     

Air-broadening parameters in the ν3 band of NO2 using a multispectrum fitting technique

Air-broadened linewidths, pressure-induced shift coefficients and their temperature dependences were retrieved for over 1000 transitions in the ν₃ band of ¹⁴N¹⁶O₂ at 6 μm. In addition, precise line center positions and relative intensities were also determined. The results were obtained by fitting simultaneously 27 spectra recorded at high resolution (0.002-0.006 cm⁻¹) with two Fourier transform spectrometers and gas sample temperatures ranging from 206 to 298 K. It was necessary to modify the multispectrum fitting software to accommodate constraints on the retrieved parameters of closely spaced spin-split doublets in order to successfully determine their broadening and shift parameters. The variations of the widths, shifts and their temperature dependences with the quantum numbers were investigated. Subsets of the observed linewidths were reproduced to within 3% using an empirical smoothing function.     

TDLAS测量CO2的温度影响修正方法研究

可调谐二极管激光吸收光谱(TDLAS)技术测量CO₂浓度时,由于测量氛围温度变化的影响引起气体吸收谱线的线强和线型发生变化,最终导致浓度测量存在较大误差。为了克服温度变化对浓度测量的影响,选用中心波长在1 580 nm的DFB激光器,基于直接吸收法,模拟电厂尾部烟道内的高浓度二氧化碳气体环境,研究了在常温(298 K)和变温(298~338 K、间隔10 K)不同温度工况下CO₂浓度的测量。结果显示,常温浓度测量的最大相对误差为-5.26%,最小相对误差为1.25%,相对误差均方值为3.39%,验证了TDLAS测量系统在常温下有着良好的测量精度和稳定性,但其在变温测量时浓度测量结果误差较大,其最大相对误差已经超过25%。为了修正温度变化对浓度测量结果的影响,适应工业测量的需要,在变温测量基础上利用最小二乘法拟合出测量系统在不同温度下的浓度与气体吸收的修正关系式。经过修正后,CO₂浓度测量的相对误差降到5%以下,相对误差均方值降到3.5%以下。修正结果表明,所提出的修正方法可以有效抑制温度变化对浓度测量结果的影响,显著提高了测量系统在变温环境下的测量精度和稳定性,为TDLAS系统测量CO₂浓度的现场应用提供了理论支持和技术保障。     

High resolution fourier transform spectrum of PD3 in the region of the stretching overtone bands 2ν1 and ν1+ν3

The infrared spectrum of the PD₃ molecule has been measured in the region of the first stretching overtone bands on a Fourier transform spectrometer with a resolution of 0.0068 cm⁻¹ and analyzed for the first time. More than 800 transitions with J^max=15 have been assigned to the bands 2ν₁ and ν₁+ν₃. An effective Hamiltonian was used which takes into account both the presence of resonance interactions between the states (2 0 0 0) and (1 0 1 0), and interactions of these with the third stretching vibrational state of the v=2 polyad, (0 0 2 0). A set of 44 spectroscopic parameters is obtained from the fit. This reproduces the 305 initial “experimental” upper rovibrational energies with an rms=0.0015 cm⁻¹.     

BeH,H2和BeH2的分子结构和势能函数

用二次组态相关(QCISD)和密度泛函(B3LYP)方法, 选用6-311++g(d,p), 6-311++g(3df,3pd)和D95(3df,3pd)基组对H₂, BeH和BeH₂分子的结构进行优化. 得到它们的基态电子态分别为H₂(¹Σ_g), BeH(²Σ)和BeH₂(¹Σ_{g 关键词： BeH 2}')" href="#">BeH₂ 2')" href="#">H₂ 二次组态相关(QCISD) 势能函数