X-ray Absorption Spectroscopy of Liquid Methanol Microjets: Bulk Electronic Structure and Hydrogen Bonding Network (original) (raw)
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Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy
The Journal of Chemical Physics, 2002
X-ray absorption spectroscopy is a powerful probe of local electronic structure in disordered media. By employing extended x-ray absorption fine structure spectroscopy of liquid microjets, the intermolecular O-O distance has been observed to undergo a 5.9% expansion at the liquid water interface, in contrast to liquid methanol for which there is a 4.6% surface contraction. Despite the similar properties of liquid water and methanol ͑e.g., abnormal heats of vaporization, boiling points, dipole moments, etc.͒, this result implies dramatic differences in the surface hydrogen bond structure, which is evidenced by the difference in surface tension of these liquids. This result is consistent with surface vibrational spectroscopy, which indicates both stronger hydrogen bonding and polar ordering at the methanol surface as a consequence of ''hydrophobic packing'' of the methyl group.
The Journal of Physical Chemistry B, 2006
Oxygen K-edge X-ray absorption spectra (XAS) of aqueous chloride solutions have been measured for Li + , Na + , K + , NH 4 + , C(NH 2 ) 3 + , Mg 2+ , and Ca 2+ at 2 and 4 M cation concentrations. Marked changes in the liquid water XAS are observed upon addition of the various monovalent cation chlorides that are nearly independent of the identity of the cation. This indicates that interactions with the dissolved monovalent cations do not significantly perturb the unoccupied molecular orbitals of water molecules in the vicinity of the cations and that water-chloride interactions are primarily responsible for the observed spectral changes. In contrast, the addition of the divalent cations engenders changes unique from the case of the monovalent cations, as well as from each other. Density functional theory calculations suggest that the ion-specific spectral variations arise primarily from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, probably as a result of differences in charge transfer from the water molecules onto the divalent cations.
Local Structures of Methanol–Water Binary Solutions Studied by Soft X-ray Absorption Spectroscopy
Journal of Physical Chemistry B, 2014
Liquid methanol shows one-and two-dimensional (1D/2D) hydrogen bond (HB) networks, and liquid water shows three-dimensional (3D) HB networks. We have clearly found three different local structures around the methyl g r o u p o f m e t h a n o l − w a t e r b i n a r y s o l u t i o n s (CH 3 OH) X (H 2 O) 1−X at different concentrations in C K-edge soft X-ray absorption spectroscopy (XAS). With the help of molecular dynamics simulations, we have discussed the concentration dependence of the hydrophobic interaction at the methyl group in the C K-edge XAS spectra. In the methanol-rich region I (1.0 > X > 0.7), a small amount of water molecules exists separately around dominant 1D/2D HB networks of methanol clusters. In the region II (0.7 > X > 0.3), the hydrophobic interaction of the methyl group is dominant due to the increase of mixed methanol−water 3D network structures. In the waterrich region III (0.3 > X > 0.05), methanol molecules are separately embedded in dominant 3D HB networks of water. On the other hand, the pre-edge feature in the O K-edge XAS shows almost linear concentration dependence. It means the HB interaction between methanol and water is almost the same as that of water−water and of methanol−methanol.
The Journal of chemical physics, 2016
While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interaction...
Investigation of volatile liquid surfaces by synchrotron x-ray spectroscopy of liquid microjets
2007
Soft x-ray absorption spectroscopy is a powerful probe of surface electronic and geometric structure in metals, semiconductors, and thin films. Because these techniques generally require ultrahigh vacuum, corresponding studies of volatile liquid surfaces have hitherto been precluded. We describe the design and implementation of an x-ray experiment based on the use of liquid microjets, permitting the study of volatile liquid surfaces under quasi-equilibrium conditions by synchrotron-based spectroscopy. The liquid microjet temperatures are also characterized by Raman spectroscopy, which connects our structural studies with those conducted on liquid samples under equilibrium conditions. In recent experiments, we have observed and quantified the intermolecular surface relaxation of liquid water and methanol and have identified a large population of ''acceptor-only'' molecules at the liquid water interface.
X-ray Spectroscopy of Liquid Water Microjets
The Journal of Physical Chemistry B, 2001
We present the first results from studies of liquid water microjets by soft X-ray absorption spectroscopy. Near the oxygen K-edge (∼530 eV) a fine-structure pattern very similar to that found for gaseous water monomers is observed when the surface-selective total ion yield (TIY) is measured, but a broadened and blue-shifted spectrum emerges when detecting the bulk-sensitive total electron yield (TEY). TIY EXAFS measurements produce a nearest neighbor O-O distance for surface molecules (3.00 Å) slightly longer than that of the isolated water dimer (2.98 Å), whereas the O-O distance extracted from TEY EXAFS corresponds to that accepted for bulk water (2.85 Å). Together, these results evidence an equilibrium liquid water surface dominated by water molecules interacting weakly at longer distances than in the bulk, thus supporting predictions from computer simulations.
The Journal of Chemical Physics, 2008
Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH 3 OH) n + were measured as the soft X-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the σ*(O-H) resonance transition, exhibits a 1.20-eV blue-shift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region.
Zeitschrift für Naturforschung A, 2000
The structure of clusters in methanol-water solutions in its dependence on the methanol mole fraction xM has been investigated by mass spectrometry on clusters isolated from submicron droplets by adiabatic expansion in vacuum and by X-ray diffraction on the bulk binary solutions. The mass spectra have shown that the average hydration number, (nm), of m-mer methanol clusters decreases with increasing xM , accompanied by two inflection points at xM = ~0.3 and ~0.7. The X-ray diffraction data have revealed a similar change in the number of hydrogen bonds per water and/or methanol oxygen atom at ~2.8 Å. On the basis of both results, most likely models of clusters formed in the binary solutions are proposed: at 0 < xM < 0.3 the tetrahedral-like water cluster is the main species, at 0.3 < xM < 0.7 chain clusters of methanol molecules gradually evolve with increasing methanol content, and finally, at xM > 7 chain clusters of methanol become predominant. The present results a...
Monomer, clusters, liquid: an integrated spectroscopic study of methanol condensation
Physical chemistry chemical physics : PCCP, 2011
We have combined static pressure, spectroscopic temperature, Fourier transform infrared spectroscopy (FTIR), and small angle X-ray scattering (SAXS) measurements to develop a detailed picture of methanol condensing from a dilute vapor-carrier gas mixture under the highly supersaturated conditions present in a supersonic nozzle. In our experiments, methanol condensation can be divided into three stages as the gas mixture expands in the nozzle. In the first stage, as the temperature decreases rapidly, small methanol n-mers (clusters) form, increase in concentration, and evolve in size. In the second stage, the temperature decreases more slowly, and the n-mer concentrations continue to rise. Thermodynamic and FTIR experiments cannot, however, definitively establish if the average cluster size is constant or if it continues to increase. Finally, when the vapor becomes supersaturated enough, liquid droplets form via nucleation and growth, consuming more monomer and reducing the concentra...
Journal of Electron Spectroscopy and Related Phenomena, 2004
We have examined the influence of the intermolecular interaction on the local electronic structure by using X-ray absorption and emission spectra of liquid methanol, water, and their mixtures (in molar ratios of 9:1 and 7:3). We find a strong involvement of hydrogen bonding in the mixing of water and methanol molecules. The local electronic structure of water and methanol clusters, where water cluster is bridging within a 6-member open-ring structured methanol cluster, is separately determined. The experimental findings suggest an incomplete mixing of water-alcohol systems and a strong self-association between methanol chain and water cluster through hydrogen bonding. The enhancement of joint water-methanol open-ring structure owes the explanation to the loss of entropy of the aqueous solutions.