Spectra Of HDO Research Articles

Atmospheric HDO Abundance Measurements in the Tibetan Plateau Based on Laser Heterodyne Radiometer

The Tibet Plateau is known as the “third pole” of the world, and its environmental change profoundly impacts East Asia and even the global climate. HDO is the stable isotope of water vapor, which acts as an ideal tracer for studying the water cycle, and which is commonly used for atmospheric circulation and climatic studies. To monitor the water vapor isotopic abundance in the Tibetan Plateau, a portable laser heterodyne radiometer was operated in Golmud in August 2019. The radiometer utilizes a narrow-linewidth 3.66 μm distributed feedback interband cascade laser as the local oscillator, the heterodyne module is been optimized and the radiometer performs with high resolution and stability in obtaining spectral data. Furthermore, the absorption spectra of atmospheric HDO and H2O are obtained, and the retrieval method for water vapor isotopic abundance is discussed. The optimal estimation method is adopted to retrieve the density of HDO and H2O. The average column density of H2O was 1.22 g/cm2, and the HDO/H2O ratio in Golmud was 178 ± 15 × 10−6 during the observation. For a better understanding of the retrieval, the retrieval errors are analyzed and compared. The results indicate that the smoothing error is significantly higher than the measurement error in this work. The backward trajectory analysis of atmospheric transport is used to investigate the relationship between water vapor density and atmospheric motion. The results indicate that the variation of H2O column density and HDO/H2O ratio have a relationship with atmospheric movements.

A global line list for HDO between 0 and 35000 cm[formula omitted] constructed using multiphoton spectra

Multiphoton spectroscopy of monodeuterated water is employed to determine more than 210 new energy levels of HDO in the 25 000–35 000 cm−1 region. These new empirical energy levels are used to fit a potential energy surface (PES) valid between 20 000 cm−1 and 35 000 cm−1. Using this PES and an accurate lower energy PES as starting points, an energy-switching surface is constructed which is capable of reproducing the whole HDO spectrum from 0 to 35 000 cm−1. This PES is used to calculate a line list for HDO which covers infra red, visible and near ultraviolet transitions.

Analysis of deuterated water contents using FTIR bending motion

Novel method for detection of heavy water in mixture has been developed based on bending vibration instead of stretching vibration. In order to apply bending motion, equation derived from equilibrium kinetics is established to find amount of HDO at equilibrium to define internal standard of analytical tool (in the concentration range of 20–80%). Based on theoretical expectation about amount of HDO and FTIR bending spectra, one can measure the initial concentration of heavy water in certain concentration range. The analytical method presented here can provide additional experimental pathway to determine exact amount of heavy water with better accuracy.

Amides as models to study the hydration of proteins and peptides — spectroscopic and theoretical approach on hydration in various temperatures

Interactions with water are one of the key factors which determine protein stability and activity in aqueous solutions. However, the protein hydration is still insufficiently understood. N-methylacetamide (NMA) is regarded as a minimal part of the peptide backbone and the relative simplicity of its structure makes it a good model for studies on protein–water interactions.In this paper, the influence of NMA and N,N-dimethylacetamide (DMA) on surrounding water molecules in a range of temperature (25–75 °C) is studied by means of the FTIR spectroscopy. The results of the difference HDO spectra method are compared with the results of theoretical DFT calculations of NMA and DMA aqueous complexes.Both NMA and DMA can be regarded as “structure-makers”, yet their hydration spheres are different. These molecules exhibit a mixed and mutually dependent types of hydration: hydrophilic and hydrophobic. In the case of a NMA molecule that has one methyl group less than DMA, the type of hydrophobic hydration is more important. The DMA hydration sphere is less stable: the interactions between water molecules around the methyl groups are strained. Moreover, the hydration of NMA is much more temperature dependant than in the case of DMA. The source of the differences may be hidden in the NH⋯H2O interaction.The delicate nature of water interactions with the peptide block models may be cautiously translated into the much more complicated interactions of proteins with their hydration shells.

Line parameters for CO2- and self-broadening in the ν3 band of HD16O

Pressure-broadened line shape parameters of transitions in the ν3 band of HDO (ν0=3707.4cm-1) were measured from spectra of HDO and mixtures of HDO and CO2 for application to accurate retrievals of HDO abundances and D/H ratios for CO2-rich planetary atmospheres of Mars and Venus. A few calculated line lists have recently been published on HDO-CO2 line shapes and their temperature dependences, but the present study represents the first laboratory measurements of those parameters in the ν3 band; Measurements for nearly 100 transitions in the ν3 band have been made. Room temperature measurements of self-broadened width and shift coefficients for all of these transitions, line mixing via off-diagonal relaxation matrix element coefficients and quadratic speed dependence parameter were measured for the majority of these transitions. All these measurements were made by simultaneously fitting eleven high-resolution spectra of HDO and HDO-CO2 mixtures at various temperatures and pressures recorded with the Bruker Fourier transform spectrometer at the Jet Propulsion Laboratory. Two specially built coolable absorption cells with path lengths of 20.38cm and 20.941m were used to contain the sample mixtures. Multispectrum nonlinear least squares fitting algorithm was employed in the analysis.Calculations using the Modified Complex Robert-Bonamy formalism (MCRB) were made for the half-width coefficients, their temperature dependences and pressure shift coefficients for the HDO–CO2 and HDO–HDO collision systems. The calculations were made for all ν3 band transitions in the 1100–4100cm-1 region on the HITRAN2012 database. Present measurements are compared with the MCRB calculations and other literature values.

A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering

In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.

Line parameters for CO2 broadening in the ν2 band of HD16O

CO2-rich planetary atmospheres such as those of Mars and Venus require accurate knowledge of CO2 broadened HDO half-width coefficients and their temperature dependence exponents for reliable abundance determination. Although a few calculated line lists have recently been published on HDO–CO2 line shapes and their temperature dependences, laboratory measurements of those parameters are thus far non-existent. In this work, we report the first measurements of CO2-broadened half-width and pressure-shift coefficients and their temperature dependences for over 220 transitions in the ν2 band. First measurements of self-broadened half-width and self-shift coefficients at room temperature are also obtained for majority of these transitions. In addition, the first experimental determination of collisional line mixing has been reported for 11 transition pairs for HDO–CO2 and HDO–HDO systems. These results were obtained by analyzing ten high-resolution spectra of HDO and HDO–CO2 mixtures at various sample temperatures and pressures recorded with the Bruker IFS-125HR Fourier transform spectrometer at the Jet Propulsion Laboratory (JPL). Two coolable absorption cells with path lengths of 20.38cm and 20.941m were used to record the spectra. The various line parameters were retrieved by fitting all ten spectra simultaneously using a multispectrum nonlinear least squares fitting algorithm.The HDO transitions in the 1100–4100cm−1 range were extracted from the HITRAN2012 database. For the ν2 and 2ν2 -ν2 bands there were 2245 and 435 transitions, respectively. Modified Complex Robert–Bonamy formalism (MCRB) calculations were made for the half-width coefficients, their temperature dependence and the pressure shift coefficients for the HDO–CO2 and HDO–HDO collision systems. MCRB calculations are compared with the measured values.

Vibrational features of confined water in nanoporous TiO2 by Raman spectra**Project supported by the National Natural Science Foundation of China (Grant Nos. 11304049 and 11264006), the Guizhou Provincial Science and Technology Foundation, China (Grant No. J[2010]2132), and the Doctor Funds of Guizhou University, China (Grant No. [2012] 020).

Raman spectra of confined water adsorbed in nanoporous TiO2 are obtained in experiment. TiO2 samples with different pore diameters under different humidity conditions are investigated. The results indicate that the symmetric vibrational mode of water molecule is destroyed when relative humidity decreases. This indicates that the interaction between water molecules and surface of TiO2 becomes stronger when the distance between water molecules and surface turns smaller, and the interaction plays a major role in depressing the symmetric vibrational peak. The spectra of confined water in TiO2 and Vycor are compared. When filling fractions are the same, their spectra show distinctions no matter whether they are in partial filling condition or in full filling condition. The spectra of HDO confined in TiO2 with different filling fractions are compared with each other. There is no clear distinction among their vibrational peaks, and the peaks mainly relate to asymmetric vibration. Therefore, the interaction between water molecules and the wall of pore decouples the symmetric vibrational mode only, and the influences on asymmetric vibrational mode show little differences among different filling fractions.

Threshold ionization spectroscopy of H2O, HDO and D2O and low-lying vibrational levels of HDO+ and D2O+

Rotationally resolved photoelectron spectra of jet-cooled H2O, HDO and D2O have been recorded near the origin of the photoionising transition following single-photon ionization using the complementary techniques of mass-analysed threshold-ionization (MATI) and pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy. A gas mixture of H2O, HDO and D2O with Ar was obtained by mixing H2O (ℓ) and D2O (ℓ) in a reservoir and bubbling Ar gas through the mixture. To unambiguously assign the photoelectron bands to H2O, HDO or D2O, the PFI-ZEKE photoelectron spectra of the mixture were compared to MATI spectra and to spectra of H2O. Analysis of the rotational structure of the origin bands (v+1 = 0, v2+ = 0, v+3 = 0) ← (v1 = 0, v2 = 0, v3 = 0) of H2O, HDO and D2O and of the transitions to the (010), (020) and (100) levels of D2O+ and the first excited level of the O–D stretching mode of HDO+ provided new information on the photoionization dynamics of water and the energy level structure of HDO+ and D2O+.

Hydration of amino acids: FTIR spectra and molecular dynamics studies.

The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions.

The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the O-D stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the O-D stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of O-D vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing O-D stretch frequency in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the O-D stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the O-D stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the O-D stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating O-D stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the O-D stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the O-D stretch mode is shown to be important and the asymmetric line shapes of the O-D stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We anticipate that this computational approach will be of critical use in interpreting linear and nonlinear vibrational spectroscopies of HDO molecule that is considered as an excellent local probe for monitoring local electrostatic and hydrogen-bonding environment in not just salt but also other confined and crowded solutions.

Submillimeter mapping of mesospheric minor species on Venus with ALMA

Millimeter and submillimeter heterodyne spectroscopy offers the possibility of probing the mesosphere of Venus and monitoring minor species and winds. ALMA presents a unique opportunity to map mesospheric species of Venus. During Cycle 0, we have observed Venus on November 14 and 15, 2011, using the compact configuration of ALMA. The diameter of Venus was 11″ and the illumination factor was about 90%. Maps of CO, SO, SO2 and HDO have been built from transitions recorded in the 335–347GHz frequency range. A mean mesospheric thermal profile has been inferred from the analysis of the CO transition at the disk center, to be used in support of minor species retrieval. Maps of SO and SO2 abundance show significant local variations over the disk and contrast variations by as much as a factor 4. In the case of SO2, the spatial distribution appears more “patchy”, i.e. shows short-scale structures apparently disconnected from day-side and latitudinal variations. For both molecules, significant changes occur over a timescale of one day. From the disk averaged spectrum of SO recorded on November 14 at 346.528GHz, we find that the best fit is obtained with a cutoff in the SO vertical distribution at 88±2km and a uniform mixing ratio of 8.0±2.0ppb above this level. The SO2 map of November 14, derived from the weaker transition at 346.652GHz, shows a clear maximum in the morning side at low latitudes, which is less visible in the map of November 15. We find that the best fit for SO2 is obtained for a cutoff in the vertical distribution at 88±3km and a uniform mixing ratio of 12.0±3.5ppb above this level. The HDO maps retrieved from the 335.395GHz show some enhancement in the northern hemisphere, but less contrasted variations than for the sulfur species maps, with little change between November 14 and 15. Assuming a typical D/H ratio of 200 times the terrestrial value in the mesosphere of Venus, we find that the disk averaged HDO spectrum is best fitted with a uniform H2O mixing ratio of 2.5±0.6ppm (corresponding to a HDO mixing ratio of 0.165±0.040ppm). We note that our spectrum is also compatible with a H2O mixing ratio of 1.5ppm in the 80–90km altitude range, and a mixing ratio of 3ppm outside this range, as suggested by the photochemical model of Zhang et al. (2012, Icarus, vol. 217, pp. 714–739). Our results are in good general agreement with previous single dish submillimeter observations of Sandor and Clancy (2005, Icarus, vol. 177, pp. 129–143), Gurwell et al. (2007, Icarus, vol. 188, p. 288), and Sandor et al. (2010, Icarus, vol. 208, pp. 49–60; 2012, Icarus, vol. 217, pp. 839–844 ) and with SPICAV/Venus Express results of Fedorova et al. (2008, J. Geophys. Res., vol. 113, p. E00B25) and Belyaev et al. (2012).

Detection of a dense clump in a filament interacting with W51e2

In the framework of the Herschel/PRISMAS Guaranteed Time Key Program, the line of sight to the distant ultracompact HII region W51e2 has been observed using several selected molecular species. Most of the detected absorption features are not associated with the background high-mass star-forming region and probe the diffuse matter along the line of sight. We present here the detection of an additional narrow absorption feature at ~70 km/s in the observed spectra of HDO, NH3 and C3. The 70 km/s feature is not uniquely identifiable with the dynamic components (the main cloud and the large-scale foreground filament) so-far identified toward this region. The narrow absorption feature is similar to the one found toward low-mass protostars, which is characteristic of the presence of a cold external envelope. The far-infrared spectroscopic data were combined with existing ground-based observations of 12CO, 13CO, CCH, CN, and C3H2 to characterize the 70 km/s component. Using a non-LTE analysis of multiple transitions of NH3 and CN, we estimated the density (n(H2) (1-5)x10^5 cm^-3) and temperature (10-30 K) for this narrow feature. We used a gas-grain warm-up based chemical model with physical parameters derived from the NH3 data to explain the observed abundances of the different chemical species. We propose that the 70 km/s narrow feature arises in a dense and cold clump that probably is undergoing collapse to form a low-mass protostar, formed on the trailing side of the high-velocity filament, which is thought to be interacting with the W51 main cloud. While the fortuitous coincidence of the dense clump along the line of sight with the continuum-bright W51e2 compact HII region has contributed to its non-detection in the continuum images, this same attribute makes it an appropriate source for absorption studies and in particular for ice studies of star-forming regions.

Selective Probing of the OH or OD Stretch Vibration in Liquid Water Using Resonant Inelastic Soft-X-Ray Scattering

High-resolution O 1s resonant inelastic x-ray scattering spectra of liquid H2O, D2O, and HDO, obtained by excitation near the preedge resonance show, in the elastic line region, well-separated multiple vibrational structures corresponding to the internal OH stretch vibration in the ground state of water. The energy of the first-order vibrational excitation is strongly blueshifted with respect to the main band in the infrared or Raman spectra of water, indicating that water molecules with a highly weakened or broken donating hydrogen bond are correlated with the preedge structure in the x-ray absorption spectrum. The vibrational profile of preedge excited HDO water is well fitted with 50%±20% greater OH-stretch contribution compared to OD, which strongly supports a preference for OH being the weakened or broken H-bond in agreement with the well-known picture that D2O makes stronger H-bonds than H2O. Accompanying path-integral molecular dynamics simulations show that this is particularly the case for strongly asymmetrically H-bonded molecules, i.e., those that are selected by preedge excitation.

Characteristics of hydration water around hen egg lysozyme as the protein model in aqueous solution. FTIR spectroscopy and molecular dynamics simulation

In this paper, the hydration of a model protein--hen egg white lysozyme in aqueous solution has been presented. The leading method used was FTIR spectroscopy with an application of a technique of semi-heavy water (HDO) isotope dilution. Analysis of spectra of HDO isotopically diluted in water solution of lysozyme allowed us to isolate HDO spectra affected by lysozyme, and thus to characterise the energetic state of water molecules and their arrangement around protein molecules. The number of water molecules and the shape of the affected HDO spectrum were obtained using a classical and a chemometric method. This shape showed that the HDO spectrum affected by lysozyme may be presented as a superposition of two spectra corresponding to HDO affected by N-methylacetamide and the carboxylate anion (of the formic acid). Moreover, based on the difference in intermolecular distances distribution of water molecules (obtained from spectral data), we demonstrated that the lysozyme molecule causes a decrease in population of weak hydrogen bonds, and concurrently increases the probability of an occurrence of short hydrogen bonds in water affected by lysozyme. This conclusion was also confirmed by the molecular dynamics (MD) simulation.

Hydration of Simple Carboxylic Acids from Infrared Spectra of HDO and Theoretical Calculations

The hydration of carboxylic acids in dilute aqueous solutions is important for our understanding of their functioning in the biochemical context. Here we apply vibrational spectra of HDO isotopically diluted in H(2)O to study this phenomenon, using the difference spectra method for analysis and interpretation of the results. The spectra of HDO affected by formic, acetic, and propionic acid display characteristic component bands, significantly red-shifted from the bulk HDO band position. The appearance of these component bands is linked with isotopic substitution on the carboxylic acid molecule, which forms a short and strong hydrogen bond with a water molecule. Additionally, a charge separation due to the proton transfer in the neutral form of the complex leading to a contact ion pair formation may be inferred from the affected HDO spectra. Apart from the contraction of the principal acid-water hydrogen bond, it results in other major structural changes in the hydration shell, as revealed by density functional theory (DFT) calculations of optimal geometries of aqueous clusters of the studied acids.

Fourier transform infrared spectroscopic and theoretical study of water interactions with glycine and its N-methylated derivatives

In this study we attempt to explain the molecular aspects of amino acids' hydration. Glycine and its N-methylated derivatives: N-methylglycine, N,N-dimethylglycine, and N,N,N-trimethylglycine were used as model solutes in aqueous solution, applying FT-IR spectroscopy as the experimental method. The quantitative version of the difference spectra method enabled us to obtain the solute-affected HDO spectra as probes of influenced water. The spectral results were confronted with density functional theory calculated structures of small hydration complexes of the solutes using the polarizable continuum model. It appears that the hydration of amino acids in the zwitterionic form can be understood allowing a synchronized fluctuation of hydrogen bonding between the solute and the water molecules. This effect is caused by a noncooperative interaction of water molecules with electrophilic groups of amino acid and by intramolecular hydrogen bond, allowing proton transfer from the carboxylic to the amine group, accomplishing by the chain of two to four water molecules. As a result, an instantaneous water-induced asymmetry of the carboxylate and the amino group of amino acid molecule is observed and recorded as HDO band splitting. Water molecules interacting with the carboxylate group give component bands at 2543 ± 11 and 2467 ± 15 cm(-1), whereas water molecules interacting with protons of the amine group give rise to the bands at 2611 ± 15 and 2413 ± 12 cm(-1). These hydration effects have not been recognized before and there are reasons to expect their validity for other amino acids.

Vibrational spectroscopic studies of N, N′-dimethylpropyleneurea–water system: Affected solvent spectra and factor analysis

FT-IR spectra of N, N′-dimethylpropyleneurea (DMPU)–water system have been measured in the 4000–500 cm −1 range by Attenuated Total Reflectance (ATR) technique in the entire composition range. The hydration of DMPU in diluted aqueous solutions has been additionally studied with transmission FT-IR spectroscopy of isotopically diluted HDO in H 2O, used as a probe of solute hydration. The spectra have been analysed with the quantitative version of the difference spectra method that leads to isolation of the spectrum of solvent affected by the presence of the solute. DMPU-affected HDO spectra provide information about the energetic state of water molecules in the hydration shell, while affected H 2O spectra additionally reflect the structural state of the water hydrogen bond network. The CO stretching band of DMPU has been used to obtain also the H 2O-affected DMPU spectrum. The affected H 2O and DMPU spectra have been determined in infinite dilution approximation, as well as for increasing concentrations of the solute. These results are confronted with factor analysis of ATR spectra, which shows the presence of three well-defined intermolecular complexes in the studied system. Presumable structures of these complexes have been proposed on the basis of Density Functional Theory (DFT) calculations of optimal cluster geometries.

Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration

Vibrational spectroscopy is an ideally suited tool for the study of solute hydration. Nevertheless, water is commonly considered by spectroscopists a difficult solvent to work with. However, by using the isotopic dilution technique, in which a small amount of D2O is introduced into H2O or vice versa with formation of semiheavy water (HDO), many technical and interpretative problems connected with measurement of infrared spectra of water may be circumvented. Particularly, the isotopic decoupling of stretching vibrational modes greatly simplifies interpretation of the spectra. Systematic studies conducted in several laboratories since the 1980s up to the present day have provided a vast amount of data, concerning mainly ionic hydration. Many of these experiments have been performed in our laboratory. The analysis method we applied is based on the quantitative version of the difference spectra technique and allows separation of the spectrum of solute-affected HDO from the bulk solvent. This review illustrates the development of vibrational spectroscopy of HDO and spectral analysis methods over the years, as well as summarizes the results obtained for ionic and nonionic solutes, including some general hydration models formulated on their basis.

High resolution X-ray emission spectroscopy of water and its assignment based on two structural motifs

We evaluate proposed interpretations of previous X-ray emission spectroscopy (XES) data on liquid water. The split peak in the lone-pair orbital region has been interpreted in terms of either two different structural motifs, tetrahedral and distorted, or as due to core-hole-induced dissociative dynamics; here we add new data on a 1:1 H 2O/D 2O isotopic mixture and additional spectrum simulations including the core-hole-induced dynamics. The XES spectrum of HDO is quite nicely reproduced as the sum of spectra of H 2O and D 2O, which we interpret as that core-hole-induced dynamics contribute only to the peak shape and do not affect the intensity ratio between tetrahedrally coordinated and distorted. We find the simulation-based interpretation of the two lone-pair peaks as being of completely different symmetries, molecular 1b 1 and dissociated 3a 1, difficult to reconcile with the experimental intensities in the 1b 2 and 3a 1 spectral regions. We report extensive theoretical simulations of spectra probing both the distance and velocity quantum distributions of the internal OH stretch; sharp features not associated with the lone-pair, that are seen when the OH stretch is treated as a classical oscillator, become smeared out when the zero-point Franck–Condon profile and momentum distribution in the v = 0 level of the OH stretch are taken into account. This demonstrates that neglecting zero-point motion in simulating XES spectra of water generates artificially sharp structures. XES spectra of 1 M and 4 M hydrochloric acid (HCl) and sodium hydroxide (NaOH) are reported. These spectra indicate that dissociated species most likely can be excluded as the origin of the double 1b 1 peak structure. We thus argue that the experimental observation of two distinct peaks in the lone-pair region is less likely to be explained by an unstructured continuum model of the liquid, but is easily explained within a two-component fluctuating model.