Evidence for the contribution of water dimers to the near-IR water vapour self-continuum

The nature of the water vapour continuum absorption and the possible contribution of water dimers (WD) to this phenomenon have been a matter of debate for many years. The current work presents an overview and analysis of a number of experiments, both recent and old, where spectral signatures, similar to recent theoretical predictions for WD, have been observed in equilibrium laboratory conditions within near-infra-red (IR) water vapour absorption bands. These experiments, in contrast to those where water complexes are usually studied in non-equilibrium and low-temperature conditions, can give direct information about the possible WD amount in atmospheric conditions. Intercomparison of the results of these works and the recent ab initio prediction for WD band intensities and positions testifies in favour of a significant contribution of WD absorption to the water vapour self-continuum in the centre of the strongest near-IR water vapour absorption bands.     

Water vapour self-continuum and water dimers: 1. Analysis of recent work

Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8-12 μm window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasi-bound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.     

IR absorption spectrum (4200–3100 cm) of H2O and (H2O)2 in CCl4. Estimates of the equilibrium constant and evidence that the atmospheric water absorption continuum is due to the water dimer

IR absorption spectra, 4200–3100 cm⁻¹, of water in CCl₄ solutions are presented. It is shown that for saturated solutions significant amounts of water are present as dimer (ca. 2%). The IR spectra of the monomer and dimer are retrieved. The integrated absorption coefficients of the monomer absorption are significantly enhanced relative to the gas phase values. The dimer spectrum consists of 5 bands, of which 4 were expected from data from cold beams and cold matrices. The origin of the “extra” band is discussed. In addition it is argued that the dimer absorption bands intensities must be enhanced relative to the gas phase values. Based on recent calculations of band strengths, and observed frequency shifts relative to the gas phase, the intensity enhancement factors are estimated as well as the monomer/dimer equilibrium constant in CCl₄ solution at T=296 K (K_c=1.29 mol⁻¹ L). It is noted that the observed dimer spectrum has a striking resemblance with the water vapour continuum determined by Burch in 1985 which was recently remeasured by Paynter et al. and it is concluded that the atmospheric water absorption continuum in the investigated spectral region must be due to water dimer. Based on the newly published spectral data a revised value of the gas phase equilibrium constant is suggested (K_p=0.035 atm⁻¹ at T=296 K) as well as a value for the standard enthalpy of formation, ΔH⁰=15.4 kJ mol⁻¹.     

Measurement of the continuum absorption coefficient of water vapor near 14400 cm−1 (0.694 μm)

The continuum absorption coefficient (CAC) of water vapor (k _cont) in the visible region is determined for the first time from the data of laboratory measurements. For this purpose, the absorption spectra of water vapor in the region 14395–14402 cm^?1 are recorded with the aid of a high-sensitivity photoacoustic spectrometer with a frequency-tunable single-pulse ruby laser, and the absorption measured in this transparency microwindow is compared with that calculated based on the HITRAN 2004 data bank. In the spectral region under study, k _cont = (0.53 ± 0.18) × 10^?9 cm^?1 mbar^?1 at a total pressure of a water vapor-nitrogen mixture of 1000 mbar and a temperature of 295 K. This value of the CAC is roughly 23% higher than the CAC value in the IO-CKD model of the continuum.     

Dependency of injection seeding and spectral purity of a single resonant KTP optical parametric oscillator on the phase matching condition

For spectroscopic and remote sensing applications injection seeded optical parametric oscillators (OPOs) are well established. In this paper we study the dependencies of signal resonant injection seeding of an OPO on its resonator length, phase matching angle and pump power in detail. The quality of the seeding process is assessed by stabilising the seed laser on a molecular absorption line of water vapour and using a water vapour absorption cell as a narrow bandwidth filter for the injection seeded radiation. A reduction of the acceptance of injection seeding is observed with increasing pump power. For small phase mismatch injection seeding with a spectral purity of 99.7% was observed at 13-fold OPO threshold. A signal pulse energy of 38 mJ with 50% pump depletion was achieved with a beam parameter M² of about 6. PACS 42.65.Yj; 42.79.Nv; 42.79.Qx     

Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800-12,000 cm⁻¹ under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800-12,000 cm⁻¹ spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000-9200 cm⁻¹ spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000-9200 cm⁻¹ spectral region) are used. This strongly suggests that the H₂O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m⁻² when using either the UCL08 or Oudot line parameters in the 8000-9200 cm⁻¹ region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500-2900 cm⁻¹ region in the observations.     

Water vapour continuum absorption at 8–13 μ

A water vapour continuum absorption in the 8–13 μ region has been investigated in the laboratory and under field conditions.     

Line shape in far wings and water vapor absorption in a broad temperature interval

Despite the long-term history of extensive studies on water vapor continuum absorption it can hardly be said that an exhaustive consideration has been given to this problem both from experimental and theoretical viewpoints. For instance, deficiency remains concerning the precise data on the absorption coefficient as a function of temperature, especially at reduced temperatures. New experimental data on water vapor continuum absorption in the 800-1250 cm⁻¹ spectral region at temperatures from 311 to 363 K have become available quite recently [15]. Two advanced variants of the line wing theory - asymptotic and quasistatic - are briefly outlined. The asymptotic line wing theory has been used successfully to describe the absorption coefficient both at elevated temperatures of the Baranov study and at the temperatures of earlier experimental data. Comparison is made with the results obtained from the quasistatic line wing theory.     

The water-vapor continuum and selective absorption in the 3-5 μm spectral region at temperatures from 311 to 363 K

The pure water-vapor continuum absorption in the 2.88 to 5.18 μm spectral region has been measured using a Fourier-transform infrared spectrometer at a resolution of 0.1 cm⁻¹. The sample temperatures and pressures varied from 311 to 363 K and from 2.8 kPa (21 Torr) to 34.5 kPa (259 Torr), respectively. The path lengths used in the study ranged from 68 to 116 m. Under these conditions, the continuum absorption in the middle of the 4 μm window is quite detectable reaching as high as 4%. The spectral processing included calculations to fit and remove the H₂O ro-vibrational structure. In the region around 5 μm, the absorption coefficients obtained are in good agreement with those of the commonly used MT_CKD continuum model. However at shorter wavelengths, the observed values significantly deviate from the model. Inspection of the present data as well as that of previous measurements leads to the conclusion that the MT_CKD model despite the latest updates significantly underestimates the rate of the continuum temperature dependence over the 4 μm atmospheric window. Line strengths for 189 H₂O transitions were obtained from the spectral processing. The deviation of these measured intensities from those listed in the HITRAN database is randomly scattered around zero to within several percents and no systematic trends were detected.     

Remote sensing of the atmosphere using ultrashort laser pulses

Theoretical and experimental studies were performed on the propagation of ultrashort optical terawatt pulses through the atmosphere. Propagation simulations of intense sub-picosecond pulses show that non-linear processes, such as white light generation, can be initiated at a chosen distance by selecting an appropriate group velocity dispersion. With this technique, a white light continuum was generated in the atmosphere whose spectral distribution was characterised in the visible and near infra-red. Applications of this novel light source for atmospheric remote sensing were investigated, combining lidar and time-resolved broadband absorption spectroscopy techniques. Measurements were performed on the oxygen molecule and water vapour. A comparison between the experimental results and the tabulated spectroscopic data led to an excellent correlation with measurements made on water vapour whereas observations on the oxygen showed discrepancy. This study demonstrates that the remote generation of a white light source represents a new way to access the range-resolved multi-trace gas analysis in the atmosphere. Received: 8 December 1999 / Revised version: 18 May 2000 / Published online: 16 August 2000     

Early stage optical emission in nanosecond laser ablation

This paper describes the results of an experimental and theoretical investigation of the physical origin of the visible continuum emission usually observed in the early stages of nanosecond laser ablation of solid materials. It has been suggested, but not confirmed that the continuum is due to radiative recombination and bremsstrahlung emission. Time and space-resolved emission spectroscopy with an absolutely calibrated spectrometer was used to study the spectral emission in laser ablation of zinc in vacuum at 4.1 J?cm^?2 using a 8 ns, 1064 nm laser pulse. By modelling the spectral emission with a spectral synthesis code, it has been shown that the continuum emission is primarily due to bound-bound transitions between strongly Stark broadened energy levels. Similarly, it can be concluded that the optical absorption is primarily due to bound-bound transitions.     

Experiments on an absorption refrigeration system powered by a solar pond

A heat source at temperatures not higher than 80°C was used to simulate the heat input to an absorption refrigerator from a solar pond. A laboratory model of an absorption refrigerator, using an ammonia-water solution at 52% concentration by weight, was operated intermittently using this heat source. Generation temperatures as high as 73°C and evaporation temperatures as low as −2°C were obtained. Tap water was used to remove the heat generated from the condensation of the ammonia vapour and the absorption of the refrigerant in the water. The temperature of the tap water was near the ambient laboratory temperature of 28°C. The COP for this unit working under such conditions was in the range 0.24–0.28.     

Calculation of solar radiation atmospheric absorption with different H2O spectral line data banks

A comparison of the atmospheric absorption calculated with different data banks of water vapour absorption lines is made. The HITRAN database, Barber-Tennyson line list (BT2), calculation of Partridge and Schwenke (PS) are considered. The contribution of H₂O lines, absent in HITRAN, to the atmospheric transmission, calculated with 10 cm⁻¹ spectral resolution in the 10 000-20 000 cm⁻¹ spectral region is up to 1.5% for a vertical path and 4% for a solar zenith angle of 70 deg. The highest difference is observed in the 940 nm band. The incoming fluxes of solar radiation, measured by a rotating solar spectroradiometer, were modeled with BT2 and HITRAN database. The difference between measured and calculated fluxes does not exceed the instrumental uncertainties.     

Millimetre wave absorption by aqueous aerosol clusters

It is shown that laboratory measurements of the anomalous millimetre wave absorption of water vapour can be interpreted as due to aqueous aerosol (Aitken) clusters. A phenomenological theory is presented which accounts for the vapour pressure and temperature dependence of existing experimental results. The relevance of the aerosol theory to the widely reported anomalous absorption in the atmosphere is discussed.     

New measurements of the water vapor continuum in the region from 0.3 to 2.7 THz

We present a spectroscopic study of the water vapor continuum absorption in the far-IR region from 10 to 90 cm⁻¹ (0.3-2.7 THz). The experimental technique combines a temperature-stabilized multipass absorption cell, a polarizing (Martin-Puplett) interferometric spectrometer, and a liquid-He-cooled bolometer detector. The contributions to the absorbance resulting from the structureless H₂O-H₂O and H₂O-N₂ continua have been measured in the temperature range from 293 to 333 K with spectral resolution of 0.04-0.12 cm⁻¹. The resonant water vapor spectrum was modeled using the HITRAN04 database and a Van Vleck-Weisskopf lineshape function with a 100 cm⁻¹ far-wing cut-off. Within experimental uncertainty, both the H₂O-H₂O and H₂O-N₂ continua demonstrate nearly quadratic dependencies of absorbance on frequency with, however, some deviation near the 2.5 THz window. The absorption coefficients of 3.83 and 0.185 (dB/km)/(kPa THz)² were measured for self- and foreign-gas continuum, respectively. The corresponding temperature exponents were found to be 8.8 and 5.7. The theoretically predicted foreign continuum is presented and a reasonable agreement with experiment is obtained.     

光谱分析的葡萄酒掺水鉴别方法

葡萄酒市场的迅猛发展,大量的中国优质葡萄酒也一直受假冒葡萄酒的侵害。假冒劣质葡萄酒的存在不仅影响中国优质葡萄酒的品牌,也会对人体产生一定的伤害。葡萄酒中掺水掺伪是制造假酒的最常见的手段,因此,对葡萄酒掺水掺伪的检测方法的研究也越来越受到国内外学者的重视。相比于传统的感官鉴定法、理化指标分析检验方法,具有快速、高效、无需破坏样本、非接触性等独特优势的可见-近红外光谱分析技术,更加适合于葡萄酒品质的快速检测。为了快速、准确的检测葡萄酒掺水问题,基于可见-近红外光谱构建了一种反映葡萄酒掺水程度的光谱吸收深度指数(DI),并设计构建了基于DI指数的葡萄酒掺水量的反演估算模型。首先采用长城解百纳葡萄酒(CC)、张裕解百纳葡萄酒(ZY)和西奥葡萄酒(XA)三种葡萄酒配制葡萄酒样本,分别提取相同量的葡萄酒作为实验对象,掺入比例为0%(未掺水的纯葡萄酒),4%,7.7%,11.1%,14.3%,17.2%的蒸馏水,获取样本共18份;另外对长城葡萄酒加大掺水比例,分别掺入比例为0%,20%,40%,60%,80%,90%的蒸馏水,获取样本数为6份,共获得24份掺有不同比例蒸馏水的葡萄酒样本。然后利用PSR-3500便携式地物光谱仪采集葡萄酒样本光谱数据,并对葡萄酒样本的原始光谱数据进行S-G滤波、特征波段选择、包络线去除等特征增强预处理;通过分析预处理后的葡萄酒样本的可见-近红外光谱特征,选取能反映葡萄酒掺水程度的837 nm处稳定的吸收特性,构建了葡萄酒掺水的光谱吸收深度指数(DI)。为了提高光谱吸收深度指数DI的稳健性,DI指数中光谱反射率的值均采用837 nm附近微小邻域均值进行计算。最后采用二次多项式拟合方法,给出了基于DI指数的葡萄酒掺水量的反演估算模型。选用长城解百纳葡萄酒在837 nm处微小邻域内光谱吸收深度指数DI值,同时选择长城葡萄酒样本中的七个样本作为模型预测集,另外4个样本作为测试集,对该葡萄酒掺水量的反演估算模型进行验证分析。实验结果表明,采用二次多项式拟合方法,该模型结果的精度R平方高达0.999 2,且该模型的估算值与真实值的平均相对误差为0.042 5,表明了基于DI指数所构建的反演估算模型不仅可以判定待鉴别葡萄酒是否掺水并且可以定量分析葡萄酒的掺水量。光谱吸收深度指数DI构建简单,且能够反映不同品牌的葡萄酒的掺水稀释程度。研究结果可为低成本、手持式简易的葡萄酒光谱检测设备的设计与研发提供科学依据,进一步促进可见-近红外光谱分析在葡萄酒品质无损检测及相关领域的应用推广。     

古尔班通古特沙漠生物土壤结皮反射光谱特征分析

通过对野外采样取得的新疆古尔班通古特沙漠中的生物土壤结皮、裸沙和干枯植被进行反射光谱测定,揭示出在干燥条件下各类地物的反射光谱特征。进一步对经过均匀喷洒0.5和1.0 mm水后的生物土壤结皮分别进行反射光谱测定,并对比分析了原始的和经水化实验后的生物土壤结皮光谱特征。依据生物土壤结皮的光谱特征,提出利用连续统去除技术估算生物土壤结皮覆盖度的方法,结果表明连续统去除光谱的负对数与生物土壤结皮盖度有很好的相关关系(r2=0.990 7)。     

Self-broadened line parameters for water vapour in the spectral region 5000-5600 cm

The self-broadening coefficients and intensities of approximately 460 of the strongest water vapour lines (intensity S ? 1.5 × 10⁻²³ cm molec⁻¹) in the spectral region 5000-5600 cm⁻¹ have been derived from new laboratory measurements. The derived line intensities are on average in a good agreement with those in HITRAN-2001 (v.11.0) (within 0.5% for total band intensity). Self-broadening coefficients are compared with values estimated from the HITRAN-2001 foreign-broadening coefficients. Comparison has been also made with the recent HITRAN-2004 (v.12.0) compilation, which revealed marked systematic differences in the self-broadening coefficients (up to 20%) and in the line intensities (up to 5%). The possible reasons for these deviations are discussed.     

Direct integration transmittance model

A transmittance model has been developed for interpretation of high spectral resolution measurements of laboratory absorption and of planetary thermal emission. The high spectral resolution requires transmittances to be computed monochromatically by summing the contribution of individual molecular absorption lines. A magnetic tape atlas of H₂O, O₃, and CO₂ molecular line parameters serves as input to the transmittance model with simple empirical representations used for continuum regions wherever suitable laboratory data exist. The theoretical formulation of the transmittance model and the computational procedures used for the evaluation of the transmittances are discussed, and application of the model to several homogenous path laboratory absorption examples is demonstrated.     

Measurements of absorption spectra of thin films by the waveguide technique

The waveguide technique for measuring the absorption spectra of thin films in spectral range of their transparency is considered. The error of measuring the absorption of a ～0.1 μm thick film does not exceed 5% at an absorption coefficient of less than 50 cm^–1. Capabilities and limitations of the method are discussed.