Raman spectroscopic study of the tellurite minerals: rajite and denningite

Tellurites may be subdivided according to formula and structure. There are five groups based upon the formulae (a) A(XO3), (b) A(XO3).xH2O, (c) A2(XO3)3.xH2O, (d) A2(X2O5) and (e) A(X3O8). Raman spectroscopy has been used to study rajite and denningite, examples of group (d). Minerals of the tellurite group are porous zeolite-like materials. Raman bands for rajite observed at 740, and 676 and 667 cm(-1) are attributed to the nu1 (Te2O5)(2-) symmetric stretching mode and the nu3 (TeO3)(2-) antisymmetric stretching modes, respectively. A second rajite mineral sample provided a more complex Raman spectrum with Raman bands at 754 and 731 cm(-1) assigned to the nu1 (Te2O5)(2-) symmetric stretching modes and two bands at 652 and 603 cm(-1) are accounted for by the nu3 (Te2O5)(2-) antisymmetric stretching mode. The Raman spectrum of dennigite displays an intense band at 734 cm(-1) attributed to the nu1 (Te2O5)(2-) symmetric stretching mode with a second Raman band at 674 cm(-1) assigned to the nu3 (Te2O5)(2-) antisymmetric stretching mode. Raman bands for rajite, observed at (346, 370) and 438 cm(-1) are assigned to the (Te2O5)(2-)nu2 (A1) bending mode and nu4 (E) bending modes.     

Raman spectroscopic study of the tellurite minerals: carlfriesite and spiroffite

Raman spectroscopy has been used to study the tellurite minerals spiroffite and carlfriesite, which are minerals of formula type A(2)(X(3)O(8)) where A is Ca(2+) for the mineral carlfriesite and is Zn(2+) and Mn(2+) for the mineral spiroffite. Raman bands for spiroffite observed at 721 and 743 cm(-1), and 650 cm(-1) are attributed to the nu(1) (Te(3)O(8))(2-) symmetric stretching mode and the nu(3) (Te(3)O(8))(2-) antisymmetric stretching modes, respectively. A second spiroffite mineral sample provided a Raman spectrum with bands at 727 cm(-1) assigned to the nu(1) (Te(3)O(8))(2-) symmetric stretching modes and the band at 640cm(-1) accounted for by the nu(3) (Te(3)O(8))(2-) antisymmetric stretching mode. The Raman spectrum of carlfriesite showed an intense band at 721 cm(-1). Raman bands for spiroffite, observed at (346, 394) and 466 cm(-1) are assigned to the (Te(3)O(8))(2-)nu(2) (A(1)) bending mode and nu(4) (E) bending modes. The Raman spectroscopy of the minerals carlfriesite and spiroffite are difficult because of the presence of impurities and other diagenetically related tellurite minerals.     

Raman and infrared spectroscopy of selected vanadates

Raman and infrared spectroscopy has been used to study the structure of selected vanadates including pascoite, huemulite, barnesite, hewettite, metahewettite, hummerite. Pascoite, rauvite and huemulite are examples of simple salts involving the decavanadates anion (V10O28)6-. Decavanadate consists of four distinct VO6 units which are reflected in Raman bands at the higher wavenumbers. The Raman spectra of these minerals are characterised by two intense bands at 991 and 965 cm(-1). Four pascoite Raman bands are observed at 991, 965, 958 and 905 cm(-1) and originate from four distinct VO6 sites. The other minerals namely barnesite, hewettite, metahewettite and hummerite have similar layered structures to the decavanadates but are based upon (V5O14)3- units. Barnesite is characterised by a single Raman band at 1010 cm(-1), whilst hummerite has Raman bands at 999 and 962 cm(-1). The absence of four distinct bands indicates the overlap of the vibrational modes from two of the VO6 sites. Metarossite is characterised by a strong band at 953 cm(-1). These bands are assigned to nu1 symmetric stretching modes of (V6O16)2- units and terminal VO3 units. In the infrared spectra of these minerals, bands are observed in the 837-860 cm(-1) and in the 803-833 cm(-1) region. In some of the Raman spectra bands are observed for pascoite, hummerite and metahewettite in similar positions. These bands are assigned to nu3 antisymmetric stretching of (V10O28)6- units or (V5O14)3- units. Because of the complexity of the spectra in the low wavenumber region assignment of bands is difficult. Bands are observed in the 404-458 cm(-1) region and are assigned to the nu2 bending modes of (V10O28)6- units or (V5O14)3- units. Raman bands are observed in the 530-620 cm(-1) region and are assigned to the nu4 bending modes of (V10O28)6- units or (V5O14)3- units. The Raman spectra of the vanadates in the low wavenumber region are complex with multiple overlapping bands which are probably due to VO subunits and MO bonds.     

Raman under nitrogen. The high-resolution Raman spectroscopy of crystalline uranocene, thorocene, and ferrocene

The utility of recording Raman spectroscopy under liquid nitrogen, a technique we call Raman under nitrogen (RUN), is demonstrated for ferrocene, uranocene, and thorocene. Using RUN, low-temperature (liquid nitrogen cooled) Raman spectra for these compounds exhibit higher resolution than previous studies, and new vibrational features are reported. The first Raman spectra of crystalline uranocene at 77 K are reported using excitation from argon (5145 A) and krypton (6764 A) ion lasers. The spectra obtained showed bands corresponding to vibrational transitions at 212, 236, 259, 379, 753, 897, 1500, and 3042 cm(-1), assigned to ring-metal-ring stretching, ring-metal tilting, out-of-plane CCC bending, in-plane CCC bending, ring-breathing, C-H bending, CC stretching and CH stretching, respectively. The assigned vibrational bands are compared to those of uranocene in THF, (COT)2-, and thorocene. All vibrational frequencies of the ligands, except the 259 cm(-1) out-of-plane CCC bending mode, were found to increase upon coordination. A broad, polarizable band centered about approximately 460 cm(-1) was also observed. The 460 cm(-1) band is greatly enhanced relative to the vibrational Raman transitions with excitations from the krypton ion laser, which is indicative of an electronic resonance Raman process as has been shown previously. The electronic resonance Raman band is observed to split into three distinct bands at 450, 461, and 474 cm(-1) with 6764 A excitation. Relativistic density functional theory is used to provide theoretical interpretations of the measured spectra.     

A Raman spectroscopic study of the uranyl sulphate mineral johannite

Raman spectroscopy at 298 and 77K has been used to study the secondary uranyl mineral johannite of formula (Cu(UO2)2(SO4)2(OH)2 x 8H2O). Four Raman bands are observed at 3593, 3523, 3387 and 3234cm(-1) and four infrared bands at 3589, 3518, 3389 and 3205cm(-1). The first two bands are assigned to OH- units (hydroxyls) and the second two bands to water units. Estimations of the hydrogen bond distances for these four bands are 3.35, 2.92, 2.79 and 2.70 A. A sharp intense band at 1042 cm(-1) is attributed to the (SO4)2- symmetric stretching vibration and the three Raman bands at 1147, 1100 and 1090cm(-1) to the (SO4)2- anti-symmetric stretching vibrations. The nu2 bending modes were at 469, 425 and 388 cm(-1) at 77K confirming the reduction in symmetry of the (SO4)2- units. At 77K two bands at 811 and 786 cm(-1) are attributed to the nu1 symmetric stretching modes of the (UO2)2+ units suggesting the non-equivalence of the UO bonds in the (UO2)2+ units. The band at 786cm(-1), however, may be related to water molecules libration modes. In the 77K Raman spectrum, bands are observed at 306, 282, 231 and 210cm(-1) with other low intensity bands found at 191, 170 and 149cm(-1). The two bands at 282 and 210 cm(-1) are attributed to the doubly degenerate nu2 bending vibration of the (UO2)2+ units. Raman spectroscopy can contribute significant knowledge in the study of uranyl minerals because of better band separation with significantly narrower bands, avoiding the complex spectral profiles as observed with infrared spectroscopy.     

Raman spectroscopy of uranyl rare earth carbonate kamotoite-(Y)

Raman spectroscopy at 298 and 77K has been used to study the mineral kamotoite-(Y), a uranyl rare earth carbonate mineral of formula Y(2)(UO(2))(4)(CO(3))(3)(OH)(8).10-11H(2)O. The mineral is characterised by two Raman bands at 1130.9 and 1124.6 cm(-1) assigned to the nu(1) symmetric stretching mode of the (CO(3))(2-) units, while those at 1170.4 and 862.3 cm(-1) (77K) to the deltaU-OH bending vibrations. The assignment of the two bands at 814.7 and 809.6 cm(-1) is difficult because of the potential overlap between the symmetric stretching modes of the (UO(2))(2+) units and the nu(2) bending modes of the (CO(3))(2-) units. Only a single band is observed in the 77K spectrum at 811.6 cm(-1). One possible assignment is that the band at 814.7 cm(-1) is attributable to the nu(1) symmetric stretching mode of the (UO(2))(2+) units and the second band at 809.6 cm(-1) is due to the nu(2) bending modes of the (CO(3))(2-) units. Bands observed at 584 and 547.3 cm(-1) are attributed to water librational modes. An intense band at 417.7 cm(-1) resolved into two components at 422.0 and 416.6 cm(-1) in the 77K spectrum is assigned to an Y(2)O(2) stretching vibration. Bands at 336.3, 286.4 and 231.6 cm(-1) are assigned to the nu(2) (UO(2))(2+) bending modes. U-O bond lengths in uranyl are calculated from the wavenumbers of the uranyl symmetric stretching vibrations. The presence of symmetrically distinct uranyl and carbonate units in the crystal structure of kamotoite-(Y) is assumed. Hydrogen-bonding network related to the presence of water molecules and hydroxyls is shortly discussed.     

Raman spectroscopy of synthetic and natural iowaite

The chemistry of a magnesium based hydrotalcite known as iowaite Mg6Fe2Cl2(OH)16.4H2O has been studied using Raman spectroscopy. Iowaite has chloride as the counter anion in the interlayer. The formula of synthetic iowaite was found to be Mg5.78Fe2.09(Cl,(CO3)0.5)(OH)16.4H2O. Oxidation of natural iowaite results in the formation of Mg4FeO(Cl,CO3) (OH)8.4H2O. X-ray diffraction (XRD) shows that the iowaite is a layered structure with a d(001) spacing of 8.0 angtsroms. For synthetic iowaite three Raman bands at 1376, 1194 and 1084 cm(-1) are attributed to CO3 stretching vibrations. These bands are not observed for the natural iowaite but are observed when the natural iowaite is exposed to air. The Raman spectrum of natural iowaite shows three bands at 708, 690 and 620 cm(-1) and upon exposure to air, two broad bands are found at 710 and 648 cm(-1). The Raman spectrum of synthetic iowaite has a very broad band at 712 cm(-1). The Raman spectrum of natural iowaite shows an intense band at 527 cm(-1). The air oxidized iowaite shows two bands at 547 and 484 cm(-1) attributed to the (CO3)(2-)nu2 bending mode. Raman spectroscopy has proven most useful for the study of the chemistry of iowaite and chemical changes induced in natural iowaite upon exposure to air.     

Raman spectroscopy of newberyite, hannayite and struvite

The phosphate minerals hannayite, newberyite and struvite have been studied by Raman spectroscopy using a thermal stage. Hannayite and newberyite are characterised by an intense band at around 980cm(-1) assigned to the v(1) symmetric stretching vibration of the HPO(4) units. In contrast the symmetric stretching mode is observed at 942cm(-1) for struvite. The Raman spectra are characterised by multiple v(3) anti-symmetric stretching bands and v(2) and v(4) bending modes indicating strong distortion of the HPO(4) and PO(4) units. Hannayite and newberyite are defined by bands at 3382 and 3350cm(-1) attributed to HOPO(3) vibrations and hannayite and struvite by bands at 2990, 2973 and 2874 assigned to NH(4)(+) bands. Raman spectroscopy has proven most useful for the analysis of these 'cave' minerals where complex paragenetic relationships exist between the minerals.     

Raman spectroscopic study of a hydroxy-arsenate mineral containing bismuth-atelestite Bi2O(OH)(AsO4)

The Raman spectrum of atelestite Bi2O(OH)(AsO4), a hydroxy-arsenate mineral containing bismuth, has been studied in terms of spectra-structure relations. The studied spectrum is compared with the Raman spectrum of atelestite downloaded from the RRUFF database. The sharp intense band at 834 cm(-1) is assigned to the ν1 AsO4(3-) (A1) symmetric stretching mode and the three bands at 767, 782 and 802 cm(-1) to the ν3 AsO4(3-) antisymmetric stretching modes. The bands at 310, 324, 353, 370, 395, 450, 480 and 623 cm(-1) are assigned to the corresponding ν4 and ν2 bending modes and BiOBi (vibration of bridging oxygen) and BiO (vibration of non-bridging oxygen) stretching vibrations. Lattice modes are observed at 172, 199 and 218 cm(-1). A broad low intensity band at 3095 cm(-1) is attributed to the hydrogen bonded OH units in the atelestite structure. A weak band at 1082 cm(-1) is assigned to δ(BiOH) vibration.     

Using Raman spectroscopy to identify mixite minerals

Raman spectroscopy has been used to identify whether or not a selection of minerals labelled as mixites (formula BiCu6(AsO4)3(OH)6.3H2O) are correctly marked. Of the four samples, two samples are shown to be potentially mixites because of the presence of the characteristic Raman spectra of (AsO4)3- units and (HAsO4)- units, characterised by bands at around 803 and 833 cm(-1). Two of the minerals are shown to be predominantly carbonates. Bands are observed at 3473.9 and 3470.3 cm(-1) for the two mixite samples. Bands observed in the region 880-910 cm(-1) and in the 867-870 cm(-1) region are assigned to the AsO stretching vibrations of (HAsO4)2- and (H2AsO4)- units. Whilst bands at around 803 and 833 cm(-1) are assigned to the stretching vibrations of uncomplexed (AsO4)3- units. Intense bands observed at 473.7 and 475.4 cm(-1) are assigned to the nu4 bending mode of AsO4 units. Bands observed at around 386.5, 395.3 and 423.1 cm(-1) are assigned to the nu2 bending modes of the HAsO4 (434 and 400 cm(-1)) and the AsO4 groups (324 cm(-1)). Raman spectroscopy lends itself to the identification of minerals on host matrices and is especially useful for the identification of mixites.     

Raman microscopy of autunite minerals at liquid nitrogen temperature

Uranyl micas are based upon (UO(2)PO(4))(-) units in layered structures with hydrated counter cations between the interlayers. Uranyl micas also known as the autunite minerals are of general formula M(UO2)2(XO4)2 x 8-12H2O where M may be Ba, Ca, Cu, Fe(2+), Mg, Mn(2+) or 1/2(HA1) and X is As or P. The structures of these minerals have been studied using Raman microscopy at 298 and 77K. Six hydroxyl stretching bands are observed of which three are highly polarised. The hydroxyl stretching vibrations are related to the strength of hydrogen bonding of the water OH units. Bands in the Raman spectrum of autunite at 998, 842 and 820 cm(-1) are highly polarised. Low intensity band at 915 cm(-1) is attributed to the nu(3) antisymmetric stretching vibration of (UO(2))(2+) units. The band at 820 cm(-1) is attributed to the nu(1) symmetric stretching mode of the (UO(2))(2+) units. The (UO(2))(2+) bending modes are found at 295 and 222 m(-1). The presence of phosphate and arsenate anions and their isomorphic substitution are readily determined by Raman spectroscopy. The collection of Raman spectra at 77K enables excellent band separation.     

Vibrational spectroscopic study of the mineral pitticite Fe, AsO4, SO4, H2O

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the determination of the structure of these minerals. Among this group of minerals is pitticite, simply described as (Fe, AsO(4), SO(4), H(2)O). In this work, the analogue of the mineral pitticite has been synthesised. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching and bending vibrations. The Raman spectrum of the pitticite analogue shows intense peaks at 845 and 837cm(-1) assigned to the AsO(4)(3-) stretching vibrations. Raman bands at 1096 and 1182cm(-1) are attributed to the SO(4)(2-) antisymmetric stretching bands. Raman spectroscopy offers a useful method for the analysis of such colloidal minerals.     

Vibrational spectroscopy of stichtite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the mineral stitchtite, a hydrotalcite of formula Mg6Cr2(CO3)(OH)16.4H2O. Two bands are observed at 1087 and 1067 cm(-1) with an intensity ratio of approximately 2.5/1 and are attributed to the symmetric stretching vibrations of the carbonate anion. The observation of two bands is attributed to two species of carbonate in the interlayer, namely weakly hydrogen bonded and strongly hydrogen bonded. Two infrared bands are found at 1457 and 1381 cm(-1) and are assigned to the antisymmetric stretching modes. These bands were not observed in the Raman spectrum. Two infrared bands are observed at 744 and 685 cm(-1) and are assigned to the nu4 bending modes. Two Raman bands were observed at 539 and 531 cm(-1) attributed to the nu2 bending modes. Importantly the band positions of the paragenically related hydrotalcites stitchtite, iowaite, pyroaurite and reevesite all of which contain the carbonate anion occur at different wavenumbers. Consequently, Raman spectroscopy can be used to distinguish these minerals, particularly in the field where many of these hydrotalcites occur simultaneously in ore zones.     

以Au/Cu纳米棒为基底的肺腺癌组织的特征表面增强拉曼光谱研究

通过金铜共混法制备了Au/Cu合金纳米棒,研究了铜掺杂对金纳米棒等离子体共振吸收和结构的影响,探究了Au/Cu合金纳米棒的等离子体共振拉曼增强效应.以Au/Cu合金纳米棒为基底对肺腺癌组织和癌旁正常组织进行了表面增强拉曼光谱检测.结果显示,癌变组织具有比癌旁正常组织更强的拉曼信号峰,位于1250,1344,1408,1568,1608和2560 cm~(-1)附近的拉曼峰分别与蛋白质的AmideⅡ氨基化合物、C—H弯曲振动、核酸中CH_3的对称变角振动、蛋白质色氨酸惰性环振动、蛋白质酰胺I谱带分子间反平行β-折叠的C—O健伸缩振动和蛋白质的巯基(S—H)伸缩振动有关,2936 cm~(-1)附近的拉曼峰为蛋白质CH_2的对称伸缩振动和CH_3的反对称伸缩振动共同作用产生.以铜掺杂的金纳米棒为基底的表面增强拉曼光谱法有望成为检测肺癌组织的有效手段.     

Raman spectroscopic study of pascoite Ca3V10O(28)·17H2O

Raman spectroscopy has been used to study the molecular structure of the vanadate mineral pascoite. Pascoite, rauvite and huemulite are examples of simple salts involving the decavanadate anion (V10O28)6-. Decavanadate consists of four distinct VO6 units which are reflected in Raman bands occurring at higher wavenumbers. The Raman spectrum of pascoite is characterised by two intense bands at 991 and 965 cm(-1). Raman bands are observed at 991, 965, 958 and 905 cm(-1) and originate from four distinct VO6 sites in the mineral structure. In the infrared spectra of pascoite, two wavenumber regions are observed between: (1) 837 and 860, and (2) between 803 and 833 cm(-1). These bands are assigned to ν3 antisymmetric stretching modes of (V10O28)6- or (V5O14)3- units. The spectrum is highly complex in the lower wavenumber region, and therefore the assignment of bands is difficult. Bands observed in the 404 to 458 cm(-1) region are assigned to the ν2 bending modes of (V10O28)6- or (V5O14)3- units. Raman bands observed in the 530-620 cm(-1) region are assigned to the ν4 bending modes of (V10O28)6- or (V5O14)3- units. The Raman spectra of the vanadates in the low wavenumber region are complex with multiple overlapping bands which are probably due to VO subunits and MO bonds.     

Raman spectroscopy of the mineral rhodonite

The mineral rhodonite an orthosilicate has been characterised by Raman spectroscopy. The Raman spectra of three rhodonites from Broken Hill, Pachapaqui and Franklin were compared and found to be similar. The spectra are characterised by an intense band at around 1000 cm(-1) assigned to the nu(1) symmetric stretching mode and three bands at 989, 974 and 936 cm(-1) assigned to the nu(3) antisymmetric stretching modes of the SiO(4) units. An intense band at around 667 cm(-1) was assigned to the nu(4) bending mode and showed additional bands exhibiting loss of degeneracy of the SiO(4) units. The low wave number region of rhodonite is complex. A strong band at 421.9 cm(-1) is attributed to the nu(2) bending mode. The spectra of the three rhodonite mineral samples are similar but subtle differences are observed. It is proposed that these differences depend upon the cationic substitution of Mn by Ca and/or Fe(2+) and Mg.     

Coherent Raman spectra of the nu1 mode of carbon suboxide

High-resolution (0.001 cm(-1)) coherent anti-Stokes Raman spectroscopy (CARS) has been used to study the nu1 symmetric CO stretching mode of the quasi-linear molecule carbon suboxide, C3O2. Q-branch transitions are seen that originate from the ground state and from thermally populated levels of the nu7 CCC bending mode, which is of unusually low frequency. The intensity variation of the Q-branch features on cooling to about 120 K in a jet expansion requires the reversal of the order of assignment given in a previous Raman study at low resolution. The identification of the nu1 sigma(g)+ <-- sigma(g)+ transition from the ground state is confirmed by the absence of J(odd) Q-branch lines in the resolved CARS spectrum. Analysis of this band in terms of a quasi-linear model gives a good fit to the observed transitions and leads to vibrational-rotational parameters (in cm(-1)) of nu1 = 2199.9773(12) and (B' - B') = -2.044(6) x 10(-4). Other transitions originating from higher nu7 levels occur at only slightly lower wavenumber values and permit the calculation of the double minimum potential in the Q7 bending coordinate. The results indicate that the ground-state barrier to linearity (21.5 cm(-1)) increases by only 0.6 cm(-1) when the CO symmetric stretch is excited.     

Resonance Raman detection of the Fe2+-C-N modes in heme-copper oxidases: a probe of the active site

Resonance Raman spectroscopy has been employed to investigate the reduced cyano complexes of cytochrome aa(3) from bovine heart and Rhodobacter sphaeroides and of cytochrome bo(3) from E. coli. In the aa(3)-type oxidases, the frequency of the Fe-CN stretching mode is located at 468 cm(-1), and the bending Fe-C-N vibration, at 500 cm(-1). The fully reduced cytochrome bo(3)-CN complex gives rise to a stretching vibration at 468 cm(-1), a bending vibration at 491 cm(-1), and a stretching C-N vibration at 2037 cm(-1). The observed differences between aa(3) and bo(3) oxidases in the frequencies of the Fe-C-N group suggest a quantitative difference in the structure of the His-heme a(3)(2+)/Cu(B)(1+) and His-heme o(3)(2+)/Cu(B)(1+) binuclear pockets upon CN- binding.     

pH-dependent Raman study of pyrrole and its vibrational analysis using DFT calculations

Raman spectra of pyrrole in aqueous medium at different pH values, 2.5, 5.5, 7.5 and 10.5 were recorded in the two spectral regions, 1,040-1,160 cm(-1) and 3,300-3,360 cm(-1) and pH dependence of the linewidth, peak position and intensity of the Raman bands corresponding to the ring breathing and symmetric nu(N-H) stretching modes were examined. A linear pH dependence of the peak positions for the ring breathing mode and a maximum at nearly neutral pH (7.5) for the symmetric nu(N-H) normal mode is observed, whereas the linewidth (FWHM) shows almost no variation with the change of pH. A slight decrease in the wavenumber position of the nu(N-H) mode at pH value >7.5 indicates that the influence of deprotonation is small, which results from a weak interaction between the reference molecule and the surrounding environment. The density functional theory (DFT) calculations were made primarily to obtain the optimized geometry and vibrational spectra of pyrrole in the ground electronic state using B3LYP functional and the highest level basis set 6-311++G(d,p). The assignments of the normal modes of pyrrole were made on the basis of potential energy distribution (PED). The calculations were also performed on protonated and deprotonated structures of pyrrole.     

Raman spectra from very concentrated aqueous NaOH and from wet and dry, solid, and anhydrous molten, LiOH, NaOH, and KOH

High-temperature, high-pressure Raman spectra were obtained from aqueous NaOH solutions up to 2NaOHH2O, with X(NaOH)=0.667 at 480 K. The spectra corresponding to the highest compositions, X(NaOH)> or =0.5, are dominated by H3O2-. An IR xi-function dispersion curve for aqueous NaOH, at 473 K and 1 kbar, calculated from the data of Franck and Charuel indicates that the OH- ion forms H3O2- by preferential H bonding with nonhydrogen-bonded OH groups. Raman spectra from wet to anhydrous, solid LiOH, NaOH, and KOH yield sharp, symmetric OH- stretching peaks at 3664, 3633, and 3596 cm(-1), respectively, plus water-related, i.e., H3O2-, peaks near LiOH, 3562 cm(-1), NaOH, 3596 cm(-1), and, KOH, 3500 cm(-1). Absence of H3O2- peaks from the solid assures that the corresponding melt is anhydrous. Raman spectra from the anhydrous melts yield OH- stretching peak frequencies: LiOH, 3614+/-4 cm(-1), 873 K; NaOH, 3610+/-2 cm(-1), 975 K; and, KOH, 3607+/-2 cm(-1), 773 K, but low-frequency asymmetry due to ion-pair interactions is present which is centered near 3550 cm(-1). The ion-pair-related asymmetry corresponds to the sole IR maximum near 3550 cm(-1) from anhydrous molten NaOH, at 623 K. Bose-Einstein correction of published low-frequency Raman data from molten LiOH revealed an acoustic phonon, near 205 cm(-1), related to restricted translation of OH- versus Li+, and an optical phonon, at 625 cm(-1) and tau approximately 0.05 ps, due to protonic precession and/or pendular motion. Strong H bonding between water and the O atom of OH- forms H3O2-, but the proton of OH- does not bond with H significantly. Large Raman bandwidths (aqueous solutions) are explained in terms of inhomogeneous broadening due to proton transfer in a double well. Vibrational assignments are presented for H3O2-.