New infrared bands of nonpolar OCS dimer and experimental frequencies for two intermolecular modes

Spectra of the nonpolar carbonyl sulfide dimer in the region of the OCS ν(1) fundamental band were observed in a slit-jet supersonic expansion. The jet was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Six new bands were observed and analyzed, all of which originate from the dimer ground vibrational state. Three were vibrational fundamentals involving the ((18)OCS)(2) and (16)OCS-(18)OCS isotopologues. They enabled an estimate to be made of the frequency of the infrared-forbidden mode corresponding to in-phase vibration of the OCS monomers in the dimer, a value needed to obtain an intermolecular vibrational frequency from one of the observed combination bands. A relatively weak b-type dimer band centered at 2103.105 cm(-1) was assigned to the OCS 4ν(2) (l = 0) bending overtone. Combination bands were observed involving the geared bend and van der Waals stretch intermolecular modes. The resulting experimental frequencies of 37.5(20) cm(-1) for the bend and 42.9727(1) cm(-1) for the stretch are in good agreement with a recent high level theoretical calculation.     

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.     

Infrared spectroscopic investigation of two isomers of the weakly bound complex OCS-(CO2)2

Vibration-rotation spectra of the OCS-(CO(2))(2) van der Waals complex were studied by means of direct infrared absorption spectroscopy. Complexes were generated in a supersonic slit-jet apparatus, and the expansion gas was probed using a rapid-scan tunable diode laser. Infrared bands were observed for two different isomeric forms of the complex. A relatively strong band centered at 2058.799 cm(-1) was assigned to the most stable isomer, which has a barrel-shaped geometry and is already known from microwave spectroscopy. A weaker infrared band centered at 2050.702 cm(-1) was assigned to a new isomeric form, observed here for the first time, which was expected on the basis of ab initio calculations. Infrared bands for seven isotopomers were recorded in an attempt to quantify the structure of the new isomer. Because it has no symmetry elements, nine parameters are needed to fully define the geometry. It was possible to determine six of these which define the relative position of the OCS monomer with respect to the CO(2) dimer fragment in the complex while the remaining three were fixed at their ab initio values. Similarities and differences between the faces of the two isomers of OCS-(CO(2))(2) and the associated dimers are discussed.     

Melting behavior of poly(3-hydroxybutyrate) investigated by two-dimensional infrared correlation spectroscopy

The melting behavior of a bacterially synthesized biodegradable polymer, poly(3-hydroxybutyrate) (PHB), was investigated by using generalized two-dimensional infrared (2D IR) correlation spectroscopy. Temperature-dependent spectral variations in the regions of the C-H stretching (3100-2850 cm(-1)), C=O stretching (1800-1680 cm(-1)), and C-O-C stretching (1320-1120 cm(-1)) bands were monitored during the melting process. The asynchronous 2D correlation spectrum for the C=O stretching band region resolved two crystalline bands at 1731 and 1723 cm(-1). The intense band at 1723 cm(-1) may be due to the highly ordered crystalline part of PHB, and the weak band at 1731 cm(-1) possibly arises from the crystalline part with a less ordered structure. These crystalline bands at 1731 and 1723 cm(-1) share asynchronous cross peaks with a band at around 1740 cm(-1) assignable to the C=O band due to the amorphous component. This observation indicates that the decreases in the crystalline components do not proceed simultaneously with the increase in the amorphous component. In the 3020-2915 cm(-1) region where bands due to the asymmetric CH3 stretching and antisymmetric CH2 stretching modes are expected to appear, eight bands are identified at 3007, 2995, 2985, 2975, 2967, 2938, 2934, and 2929 cm(-1). The bands at 2985 and 2938 cm(-1) are ascribed to the amorphous part while the rest come from crystal field splitting, which is a characteristic of polymers with a helical structure.     

Spectroscopic observation and structure of CS2 dimer

Infrared spectra of the CS(2) dimer are observed in the region of the CS(2) ν(3) fundamental band (～1535 cm(-1)) using a tunable diode laser spectrometer. The weakly bound complex is formed in a pulsed supersonic slit-jet expansion of a dilute gas mixture of carbon disulfide in helium. Contrary to the planar slipped-parallel geometry previously observed for (CO(2))(2), (N(2)O)(2), and (OCS)(2), the CS(2) dimer exhibits a cross-shaped structure with D(2d) symmetry. Two bands were observed and analyzed: the fundamental (C-S asymmetric stretch) and a combination involving this mode plus an intermolecular vibration. In both cases, the rotational structure corresponds to a perpendicular (ΔK = ±1) band of a symmetric rotor molecule. The intermolecular center of mass separation (C-C distance) is determined to be 3.539(7) A?. Thanks to symmetry, this is the only parameter required to characterize the structure, if the monomer geometry is assumed to remain unchanged in the dimer. From the band centers of the fundamental and combination band an intermolecular frequency of 10.96 cm(-1) is obtained, which we assign as the torsional bending mode. This constitutes the first high resolution spectroscopic investigation of CS(2) dimer.     

Application of near infrared spectroscopy for the determination of adsorbed p-nitrophenol on HDTMA organoclay--implications for the removal of organic pollutants from water

NIR spectroscopy has been used to measure the adsorption of p-nitrophenol on untreated montmorillonite and surfactant exchanged montmorillonite. p-Nitrophenol is characterised by an intense NIR band at 8890 cm(-1) which shifts to 8840 cm(-1) upon adsorption on organoclay. The band was not observed for p-nitrophenol adsorbed on untreated montmorillonite. Both the montmorillonite and the surfactant modified montmorillonite are characterised by NIR bands at 7061 and 6791 cm(-1). The organoclay is characterised by two prominent bands at 5871 and 5667 cm(-1) assigned to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). A band at 6017 cm(-1) is attributed to the p-nitrophenol adsorbed on the organoclay. The band is not observed for the montmorillonite with adsorbed p-nitrophenol. It is concluded that p-nitrophenol is adsorbed to significantly greater amounts on the organoclay compared with the untreated montmorillonite. The implication is that organoclays are most useful for removing organic molecules from water through adsorption.     

Infrared and infrared emission spectroscopy of the zinc carbonate mineral smithsonite

Infrared emission and infrared spectroscopy has been used to study a series of selected natural smithsonites from different origins. An intense broad infrared band at 1440cm(-1) is assigned to the nu(3) CO(3)(2-) antisymmetric stretching vibration. An additional band is resolved at 1335cm(-1). An intense sharp Raman band at 1092cm(-1) is assigned to the CO(3)(2-) symmetric stretching vibration. Infrared emission spectra show a broad antisymmetric band at 1442cm(-1) shifting to lower wavenumbers with thermal treatment. A band observed at 870cm(-1) with a band of lesser intensity at 842cm(-1) shifts to higher wavenumbers upon thermal treatment and is observed at 865cm(-1) at 400 degrees C and is assigned to the CO(3)(2-)nu(2) mode. No nu(2) bending modes are observed in the Raman spectra for smithsonite. The band at 746cm(-1) shifts to 743cm(-1) at 400 degrees C and is attributed to the CO(3)(2-)nu(4) in phase bending modes. Two infrared bands at 744 and around 729cm(-1) are assigned to the nu(4) in phase bending mode. Multiple bands may be attributed to the structural distortion ZnO(6) octahedron. This structural distortion is brought about by the substitution of Zn by some other cation. A number of bands at 2499, 2597, 2858, 2954 and 2991cm(-1) in both the IE and infrared spectra are attributed to combination bands.     

Synthetic deuterated erythrite--a vibrational spectroscopic study

A comparison of deuterated and non-deuterated erythrite has been made using a combination of infrared and Raman spectroscopy. Infrared spectrum shows bands at 3442, 3358, 3194 and 3039 cm(-1). The band at 3442 cm(-1) is attributed to weakly hydrogen bonded water and the band at 3039 cm(-1) to strongly hydrogen bonded water. Deuteration results in the observation of OD bands at 2563, 2407 and 2279 cm(-1). The ratio of these bands change with deuteration. Deuteration shows that the strongly hydrogen bonded water is replaced in preference to the weakly hydrogen bonded water. Three HOH bending modes are observed at 1686, 1633, 1572 and DOD bending modes at 1236, 1203 and 1176 cm(-1). Deuteration causes the loss of intensity of the bands at 841, 710 and 561 cm(-1) and new bands are observed at 692, 648 and 617 cm(-1). These three bands are attributed to the water librational modes. Deuteration results in an additional Raman band at 809 cm(-1) with increasing intensity with extent of deuteration. Deuteration results in the shift of Raman bands to lower wavenumbers.     

Towards a single crystal Raman spectrum of kaolinite at 77 K

The Raman spectra at 77 K of the hydroxyl stretching of kaolinite were obtained along the three axes perpendicular to the crystal faces. Raman bands were observed at 3616, 3658 and 3677 cm(-1) together with a distinct band observed at 3691 cm(-1) and a broad profile between 3695 and 3715 cm(-1). The band at 3616 cm(-1) is assigned to the inner hydroxyl. The bands at 3658 and 3677 cm(-1) are attributed to the out-of-phase vibrations of the inner surface hydroxyls. The Raman spectra of the in-phase vibrations of the inner-surface hydroxyl-stretching region are described in terms of transverse and longitudinal optic splitting. The band at 3691 cm(-1) is assigned to the transverse optic and the broad profile to the longitudinal optic mode. This splitting remained even at liquid nitrogen temperature. The transverse optic vibration may be curve resolved into two or three bands, which are attributed to different types of hydroxyl groups in the kaolinite.     

An infrared study of CO adsorption on silica-supported Ru-Sn catalysts

CO adsorption on Ru-Sn/SiO(2) catalysts of various Sn/(Ru+Sn) ratios was examined by Diffuse Reflectance Infrared Fourier-Transform Spectroscopy (DRIFTS). The catalysts were prepared by the incipient wetness impregnation method. Catalysts were activated by H(2) reduction at 773 K. CO adsorbed on the catalysts shows spectra whose band frequencies are divided into three groups: (i) High Frequency Region (HFR), containing a band at 2065 cm(-1), (ii) Low Frequency Region 1 (LFR(1)), containing bands at 2040-2015 cm(-1), (iii) Low Frequency Region 2 (LFR(2)), containing bands at 1990 and 1945 cm(-1). The types of adsorbed CO species formed strongly depend on the ratio Sn/(Ru+Sn) in the catalyst, CO pressure and temperature of adsorption. Adsorption of CO on Ru sites in the Ru/SiO(2) catalyst results in LFR(1) bands at 2040-2015 cm(-1), which are independent of the CO pressure but the adsorption complexes are easily destroyed by raising the temperature. The addition of Sn to the catalyst creates new sites for CO adsorption. After adsorption at 298 K, the HFR band at 2065 cm(-1) and LFR(2) bands at 1990-1950 cm(-1) are observed. The relative intensities of these bands increase with increasing Sn-content in the samples. The LFR bands are thermally stable while the HFR band is not. The formation of the corresponding species is favored by increasing the CO pressure. Adsorbed CO species giving LFR(1) bands are assigned to linearly-adsorbed CO on the Ru(0) and/or on the Ru-Sn alloy sites. Adsorbed CO species giving HFR bands are assigned to CO adsorption on Ru(delta+)-O-Sn sites. After low temperature CO adsorption on samples with high Sn-content, only species that show bands at 1990 and 1945 cm(-1) in LFR(2) are observed.     

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.     

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.     

Ion core structure in (C(2)n+ and (CS2)n- (n=3-10) studied by infrared photodissociation spectroscopy

Infrared photodissociation spectra of (CS(2))(n) (+) and (CS(2))(n) (-) with n=3-10 are measured in the 1100-2000 cm(-1) region. All the (CS(2))(n) (+) clusters exhibit three bands at approximately 1410, approximately 1490, and approximately 1540 cm(-1). The intensity of the 1540 cm(-1) band relative to those of the other bands increases with increasing the cluster size, indicating that the band at 1540 cm(-1) is assignable to the antisymmetric CS stretching vibration of solvent CS(2) molecules in the clusters. On the basis of density functional theory calculations, the 1410 and 1490 cm(-1) bands of (CS(2))(n) (+) are assigned to CS stretching vibrations of the C(2)S(4) (+) cation core with a C(2) form. The (CS(2))(n) (-) clusters show two bands at around 1215 and 1530 cm(-1). Similar to the case of cation clusters, the latter band is ascribed to the antisymmetric CS stretching vibration of solvent CS(2) molecules. Vibrational frequency analysis of CS(2) (-) and C(2)S(4) (-) suggests that the 1215 cm(-1) band is attributed to the antisymmetric CS stretching vibration of the CS(2) (-) anion core with a C(2v) structure.     

Ultraviolet absorption and vibrational spectra of 2-fluoro-5-bromopyridine

The ultraviolet absorption spectrum in the range 340-185 nm in the vapour and solution phase has been measured for 2-fluoro-5-bromopyridine. Three fairly intense band systems identified as the pi* <-- pi transitions II, III and IV have been observed. A detailed vibronic analysis of the vapor and solution spectra is presented. The first system of bands is resolved into about sixty-two distinct vibronic bands in the vapour-phase spectrum. The 0,0 band is located at 35944 cm(-1). Two well-developed progressions, in which the excited state frequencies nu'25 (283 cm(-1)) and nu'19 (550 cm(-1)) are excited by several quanta, have been observed. The corresponding excited state vibrational and anharmonicity constants are found to be omega'i = 292 cm(-1), x'ii = 4.5 cm(-1) (i = 25) and omega'i = 563.8 cm(-1), x'ii = 6.9 cm(-1) (i = 19). The other two band systems show no vibronic structure, the band maxima being located at 48346 and 52701 cm(-1), respectively. The oscillator strength of the band systems in different solutions and the excited state dipole moments associated with the first two transitions have been determined by the solvent-shift method. The infrared spectrum in the region 4000-130 cm(-1) and the laser Raman spectrum of the molecule in the liquid state have been measured and a complete vibrational assignment of the observed frequencies is given. A correlation of the ground and excited state fundamental frequencies observed in the UV absorption spectrum with the Raman or infrared frequencies is presented.     

Near-infrared spectroscopic study of [AlO4Al12(OH)23(H2O)12]7+-O-Si(OH)3 nitrate crystals formed by forced hydrolysis of Al3+ in the presence of TEOS

The polymer [AlO4Al12(OH)23(H2O)12]7+-O-Si(OH)3 was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.0 in the presence of monomeric orthosilicic acid. Crystalline material was obtained by slow evaporation. Although the near-infrared spectra of the Al13-sulfate and Al13-O-Si(OH)3 are very similar, there are differences related to the bonding of the -O-Si(OH)3 group to the Al13-unit. The strong complex of bands around 7000 cm(-1) associated with the overtones and combination bands of the OH-stretching modes for Al13-sulfate is much weaker for Al13-O-Si(OH)3 and the opposite is true for the complex of bands around 5000 cm(-1) associated with the water overtone and combination modes, suggesting that the outer OH-groups of the Al13-unit are involved in the formation of the new Al13-O-Si(OH)3 units. A weak band around 7370-7631 cm(-1) is interpreted as the overtone of the Si-OH stretching vibration around 3740 cm(-1). A low intensity band, absent for Al13-sulfate and -nitrate is observed around 5550-5570 cm(-1) and is interpreted as the overtone of the OH-stretching mode of the OH-groups in the vicinity of the central AlO4 in the Al13-unit around 2890-2935 cm(-1). The interaction between the -O-Si(OH)3 group and the Al13-unit has a small influence on other bands like the combination modes of water in the 4400-4800 cm(-1) region, which show a small shift towards higher wavenumbers. The internal OH-groups in the Al13-complex are relatively shielded by the water molecules and therefore do not reflect the influence of the -O-Si(OH)3 in their band positions.     

Raman microscopy of selected tungstate minerals

A series of tungstate bearing minerals including scheelite, stolzite, ferberite, hübnerite, wolframite, russellite, tungstenian wulfenite and cuprotungstite have been analyzed by Raman microscopy. The results of the Raman spectroscopic analysis are compared with published data. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the pargenetic relationships between the minerals. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra. The nu1(Ag) band is observed at 909 cm(-1) and although the corresponding nu1(Bu) vibration should be inactive a minor band is observed around 894 cm(-1). The bands at 790 and 881 cm(-1) are associated with the antisymmetric and symmetric Ag modes of terminal WO2. The band at 695 cm(-1) is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The nu4(Eg) band was absent for scheelite. The bands at 353 and 401 cm(-1) are assigned as either deformation modes or as r(Bg) and delta(Ag) modes of terminal WO2. The band at 462 cm(-1) has an equivalent band in the infrared at 455 cm(-1) assigned as delta(as)(Au) of the (W2O4)n chain. The band at 508 cm(-1) is assigned as nu(sym)(Bg) of the (W2O4)n chain.     

Raman and infrared spectroscopy of the manganese arsenate mineral allactite

The mineral allactite [Mn(7)(AsO(4))(2)(OH)(8)] is a basic manganese arsenate which is highly pleochroic. The use of the 633 nm excitation line enables quality spectra of to be obtained irrespective of the crystal orientation. The mineral is characterised by a set of sharp bands in the 770-885 cm(-1) region. Intense and sharp Raman bands are observed at 883, 858, 834, 827, 808 and 779 cm(-1). Collecting the spectral data at 77K enabled better band separation with narrower bandwidths. The observation of multiple AsO(4) stretching bands indicates the non-equivalence of the arsenate anions in the allactite structure. In comparison the infrared spectrum shows a broad spectral profile with a series of difficult to define overlapping bands. The low wavenumber region sets of bands which are assigned to the nu(2) modes (361 and 359 cm(-1)), the nu(4) modes (471, 452 and 422 cm(-1)), AsO stretching vibrations at 331 and 324 cm(-1), and bands at 289 and 271 cm(-1) which may be ascribed to MnO stretching modes. The observation of multiple bands shows the loss of symmetry of the AsO(4) units and the non-equivalence of these units in the allactite structure. The study shows that highly pleochroic minerals can be studied by Raman spectroscopy.     

Vibrational analysis of hydroxyacetone

In order to be able to fully understand the vibrational dynamics of monosaccharide sugars, we started with hydroxyacetone CH2OHCOCH3, and glycolaldehyde CH2OHCOH, which are among the smallest molecules that contain hydroxyl and carbonyl group on neighboring carbon atoms. This sterical configuration is characteristic for saccharides and determines their biochemical activity. In this work vibrational analysis of hydroxyacetone was undertaken by performing the normal coordinate analysis for glycolaldehyde first, and transferring these force constants to hydroxyacetone. The observed Raman and infrared bands for 90 wt.% solution of hydroxyacetone in water (acetol) were used as a first approximation for the bands of free hydroxyacetone. The number of observed Raman and infrared bands for acetol exceeds the number of calculated values for the most stable hydroxyacetone conformer with Cs symmetry, which suggests more than one conformer of hydroxyacetone in water solution. In particular, there are two bands both in infrared (1083 and 1057 cm(-1)) and in Raman spectrum (1086.5 and 1053 cm(-1)) that are assigned to the CO stretching mode and this is one of the indicators of several hydroxyacetone conformers in the solution. Additional information was obtained from low temperature Raman spectra: at 240 K a broad asymmetric band centered around 280 cm(-1) appears, suggesting a disorder in the orientation of hydroxyl groups. Glassy state forms at approximately 150K. The broad band at 80 cm(-1) is assigned to frozen torsions of hydroxymethyl groups.     

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.