Infrared spectra of the (H2O)n-SO2 complexes in argon matrices

The infrared spectra of the (H(2)O)n-SO(2) complexes trapped in argon matrices have been investigated using Fourier transform infrared spectroscopy. In addition to the 1:1 and 2:1 complexes, the first spectroscopic evidence for the 3:1 complex has been obtained from the spectra of the SO stretching and the OH stretching modes. The observed frequency shifts in the bonded OH stretching region indicate that the hydrogen bonds of the 2:1 and 3:1 complexes are strengthened compared to that of the 1:1 complex, which suggests the cyclic structure of the complexes.     

Infrared spectra of CO2-doped hydrogen clusters, (H2)N-CO2

Clusters of para-H(2) and/or ortho-H(2) containing a single carbon dioxide molecule are studied by high resolution infrared spectroscopy in the 2300 cm(-1) region of the CO(2) ν(3) fundamental band. The (H(2))(N)-CO(2) clusters are formed in a pulsed supersonic jet expansion from a cooled nozzle and probed using a rapid scan tunable diode laser. Simple symmetric rotor type spectra are observed with little or no resolved K-structure, and prominent Q-branch features for ortho-H(2) but not para-H(2). Observed rotational constants and vibrational shifts are reported for ortho-H(2) up to N = 7 and para-H(2) up to N = 15, with the N > 7 assignments only made possible with the help of theoretical simulations. The para-H(2) cluster with N = 12 shows clear evidence for superfluid effects, in good agreement with theory. The presence of larger clusters with N > 15 is evident in the spectra, but specific assignments are not possible. Mixed para- + ortho-H(2) cluster transitions are well predicted by linear interpolation between corresponding pure cluster line positions.     

Infrared absorptions of the H(2)O ... H(2) complex trapped in solid neon

When a sample of neon to which have been added less than 1% each of H(2) and H(2)O is deposited at 4.3 K, the infrared spectrum of the resulting solid includes an absorption by the vibrational fundamental of H(2), which is normally infrared inactive. New absorptions are also associated with the vibrational fundamentals of the H(2)O in the sample. Similar results are obtained for deuterium-enriched samples. The new peaks are assigned to the van der Waals complex of H(2)O with H(2). As has been found in earlier theoretical, gas-phase, and solid-state studies of this and closely related systems, the infrared absorptions arise principally from complexes involving ortho-H(2), for which J=1.     

Infrared spectra of the WH4(H2)4 complex in solid hydrogen

The codeposition of laser-ablated tungsten atoms with neat hydrogen at 4 K forms a single major product with a broad 2500 cm(-1) and sharp 1860, 1830, 1782, 1008, 551, and 437 cm(-1) absorptions, which are assigned to the WH4(H2)4 complex on the basis of isotopic shifts and agreement with isotopic frequencies calculated by density functional theory. This D2d structured complex was computed earlier to form exothermically from W atoms and hydrogen molecules. Annealing the matrix allows hydrogen to evaporate and the complex to aggregate and ultimately to decompose. Comparison of the H-H stretching mode at 2500 cm(-1) and the W-H2 stretching mode at 1782 cm(-1) with 2690 and 1570 cm(-1) values for the Kubas complex W(CO)3(PR3)2(H2) suggests that the present physically stable WH4(H2)4 complex has more strongly bound dihydrogen ligands. Our CASPT2 calculations suggest a 15 kcal/mol average binding energy per dihydrogen molecule in the WH4(H2)4 complex.     

Infrared spectroscopy of Mn+ (H2O) and Mn2+ (H2O) via argon complex predissociation

Singly and doubly charged manganese-water cations, and their mixed complexes with attached argon atoms, are produced by laser vaporization in a pulsed nozzle source. Complexes of the form Mn(+)(H(2)O)Ar(n) (n = 1-4) and Mn(2+)(H(2)O)Ar(4) are studied via mass-selected infrared photodissociation spectroscopy, detected in the mass channels corresponding to the elimination of argon. Sharp resonances are detected for all complexes in the region of the symmetric and asymmetric stretch vibrations of water. With the guidance of density functional theory computations, specific vibrational band resonances are assigned to complexes having different argon attachment configurations. In the small singly charged complexes, argon adds first to the metal ion site and later in larger clusters to the hydrogens of water. The doubly charged complex has argon only on the metal ion. Vibrations in all of these complexes are shifted to lower frequencies than those of the free water molecule. These shifts are greater when argon is attached to hydrogen and also greater for the dication compared to the singly charged species. Cation binding also causes the IR intensities for water vibrations to be much greater than those of the free water molecule, and the relative intensities are greater for the symmetric stretch than the asymmetric stretch. This latter effect is also enhanced for the dication complex.     

Infrared spectra of H(2)16O, H(2)18O and D(2)O in the liquid phase by single-pass attenuated total internal reflection spectroscopy

Mid-infrared attenuated total internal reflection (ATR) spectra of H(2)16O, H(2)18O and D(2)16O in the liquid state were obtained and normal coordinate analysis was performed based on the potential energy surface obtained from density functional theory (DFT) calculations. Fits of the spectra to multiple Gaussians showed a consistent fit of three bands for the bending region and five bands for the stretching region for three isotopomers, H(2)16O, H(2)18O and D(2)16O. The results are consistent with previous work and build on earlier studies by the inclusion of three isotopomers and mixtures using the advantage of single-pass ATR to obtain high quality spectra of the water stretching bands. DFT calculation of the vibrational spectrum of liquid water was conducted on seven model systems, two systems with periodic boundary conditions (PBC) consisting of four and nine H(2)16O molecules, and five water clusters consisting of 4, 9, 19, 27 and 32 H(2)16O molecules. The PBC and cluster models were used to obtain a representation of bulk water for comparison with experiment. The nine-water PBC model was found to give a good fit to the experimental line shapes. A difference is observed in the broadening of the water bending and stretching vibrations indicative of a difference in the rate of pure dephasing. The nine-water PBC calculation was also used to calculate the wavenumber shifts observed in the water isotopomers.     

Infrared spectra of Li2SeO4.H2O,Li2SO4.H2O and Li2(S,Se)O4.H2O

On of the hydrogen bonds formed by water molecules in lithium selenate monohydrate is evidently stronger than in the corresponding sulfate, whereas the other one is weaker. The temperature dependence of the stretching and bending modes of water is similar in both compounds, their frequencies decreasing on lowering the temperature. The study of mixed sulfate—selenate compounds made it possible to clearly show that the effective symmetry of the tetrahedral ions is higher than their local crystallographic one.     

OH stretch IR spectra of (H2O)3 and benzene-(H2O)3

The OH stretch IR spectrum of (H₂O)₃ is significantly altered upon complexation of the cluster with a benzene molecule. Theoretical calculations show that the differences in the OH stretch spectra of (H₂O)₃ and benzene-(H₂O)₃ are primarily due to mode localization induced by the benzene molecule. Received: 27 January 1997 / Accepted: 28 January 1997     

Infrared and polarized Raman spectra of (CH3)2NH2Al(SO4)2 x 6H2O

FTIR and single crystal Raman spectra of (CH3)2NH2Al(SO4)2 x 6H2O have been recorded at 300 and 90 K and analysed. The shifting of nu1 mode to higher wavenumber and its appearance in Bg species contributing to the alpha(xz) and alpha(yz) polarizability tensor components indicate the distortion of SO4 tetrahedra. The presence of nu1 and nu2 modes in the IR spectrum and the lifting of degeneracies of nu2, nu3, and nu4 modes are attributed to the lowering of the symmetry of the SO4(2-) ion. Coincidence of the IR and Raman bands for different modes suggest that DMA+ ion is orientationally disordered. One of the H atoms of the NH2 group of the DMA+ ion forms moderate hydrogen bonds with the SO4(2-) anion. Al(H2O)6(3+) ion is also distorted in the crystal. The shifting of the stretching modes to lower wavenumbers and the bending mode to higher wavenumber suggest that H2O molecules form strong hydrogen bonds with SO4(2-) anion. The intensity enhancement and the narrowing of nu1SO4, deltaC2N and Al(H2O)6(3+) modes at 90 K confirm the settling down of the protons in the hydrogen bonds formed with H2O molecules and NH2 groups. This may be one of the reasons for the phase transition observed in the crystal.     

Rydberg series in the absorption spectra of H2O and D2O in the vacuum ultraviolet

The photoabsorption cross section of molecular H₂O and D₂O has been determined in the range from hν = 10eV to 20 eV with 0.03 Å resolution. A refined analysis of the Rydberg series including the rotational line shapes of several bands to locate the band origins and a comparison with recent ab initio calculations is given. In the region of continuous absorption we have assigned a p-type and an s-type Rydberg series leading to the ²A₁ and the ²B₂ state respectively with quantum defects δ ≈ 0.75 and δ ≈ 1.36.     

Infrared spectra of the water-nitrogen complexes (H2O)2-(N2)n(n = 1-4) in argon matrices

The infrared spectra of the water-nitrogen complexes trapped in argon matrices have been studied with Fourier transform infrared absorption spectroscopy. The absorption lines of the H20-N2 1:1, 1:2, 1:n, and 2:1 complexes have been confirmed on the basis of the concentration effects. In addition, we have observed a few lines and propose the assignments for the 2:2, 2:3, and 2:4 complexes in the nu1 symmetric stretching and nu2 bending regions of the proton-acceptor molecule, and in the bonded OH stretching region of the proton-donor molecule. The redshifts in the bonded OH stretching mode and blueshifts in the OH bending mode suggest that the hydrogen bonds in the (H2O)2-(N2)n complexes with n = 1-4 are strengthened by the cooperative effects compared to the pure H2O dimer. Two absorption bands due to the 3:n complexes are also observed near the bonded OH stretching region of the H2O trimer.     

Synthesis of a transition metal-dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5)

The reaction of Na[η⁵-C₅H₅Fe(CO)₂] with large excess of SO₂ in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η⁵-C₅H₅)(CO)₂FeS(O)₂S(O)₂Fe(CO)₂(η⁵-C₅H₅).     

Infrared spectroscopy of Sc(+)(H(2)O) and Sc(2+)(H(2)O) via argon complex predissociation: The charge dependence of cation hydration

Singly and doubly charged scandium-water ion-molecule complexes are produced in a supersonic molecular beam by laser vaporization. These ions are mass analyzed and size selected in a specially designed reflectron time-of-flight spectrometer. To probe their structure, vibrational spectroscopy is measured for these complexes in the O-H stretching region using infrared laser photodissociation and the method of rare gas atom predissociation, also known as "tagging." The O-H stretches in these systems are shifted to lower frequency than those for the free water molecule, and the intensity of the symmetric stretch band is strongly enhanced relative to the asymmetric stretch. These effects are more prominent for the doubly charged ions. Partially resolved rotational structure for the Sc(+)(H(2)O)Ar complex shows that the H-O-H bond angle is larger than it is in the free water molecule. Fragmentation and spectral patterns indicate that the coordination of the Sc(2+) ion is filled with six ligands (one water and five argons).     

双核钼(O)配合物[(C2H5)4N]2[Mo2(CO)8(SCH2CO2(C2H5)2]的合成, 结构, 光谱和反应性能研究

Et4NI,NaSCH2CO2C2H5和Mo(CO)6在乙腈中反应制得一种新的双核钼(0)配合物[Et4N]2-[Mo2(CO)8(SCH2CO2Et)2](1), 电化学和反应性能研究指出1在电位～-0.43V发生一有趣的双电子一步氧化, 产生[Mo2(CO)8(SCH2CO2Et)2], 若氧化反应在配位溶剂中进行, 则其部分羰基被配位溶剂分子所取代成为[Mo2(CO)6(SCH2CO2Et)2L2](L=CH3CN).在1中, Mo…Mo不存在金属键以及MoS2Mo核骨架完全不同于氧化的产物Mo(I)配合物. 这结果完全证实了双电子一步转移是由于双金属中心的金属-金属键的形成或断裂伴随桥联双金属中心结构的重排而产生的推断.     

Infrared spectra of the C2H2-(OCS)2 van der Waals complex: observation of a structure with C2 symmetry

Infrared spectra of the C(2)H(2)-(OCS)(2) trimer are studied by means of direct infrared absorption spectroscopy. The van der Waals complexes are generated in a supersonic slit-jet apparatus and probed using a rapid-scan tunable diode laser in the region of the ν(1) fundamental vibration of the OCS monomer. Two infrared bands are analyzed for the lowest energy isomer of the trimer, which has C(2) symmetry and is experimentally observed here for the first time. A relatively strong band centered at 2068.93 cm(-1) is assigned as the out-of-phase vibrations of the pair of equivalent OCS monomers. This band is blue-shifted relative to the free OCS monomer but with a reduced shift as compared with the analogous vibration of the nonpolar OCS dimer. A weaker red-shifted band observed at 2049.64 cm(-1) establishes the nonplanarity of the OCS dimer subunit within the trimer. Spectra for three isotopologues in addition to the normal form are used to help define an experimental structure, which agrees well with past and present semiempirical calculations.