Structure, energy, and IR spectra of I2*-.nH2O clusters (n=1-8): a theoretical study

The authors report theoretical results on structure, bonding, energy, and infrared spectra of iodine dimer radical anion hydrated clusters, I(2) (-).nH(2)O (n=1-8), based on a systematic study following density functional theory. Several initial guess structures are considered for each size cluster to locate minimum energy conformers with a Gaussian 6-311++G(d,p) split valence basis function (triple split valence 6-311 basis set is applied for iodine). It is observed that three different types of hydrogen bonded structures, namely, symmetrical double hydrogen bonding, single hydrogen bonding, and interwater hydrogen bonding structures, are possible in these hydrated clusters. But conformers having interwater hydrogen bonding arrangements are more stable compared to those of double or single hydrogen bonded structures. It is also noticed that up to four solvent H(2)O units can reside around the solute in interwater hydrogen bonding network. At the maximum six H(2)O units are independently linked to the dimer anion having four double hydrogen bonding and two single hydrogen bonding, suggesting the hydration number of I(2) (-) to be 6. However, conformers having H(2)O units independently linked to the iodine dimer anion are not the most stable structures. In all these hydrated clusters, the odd electron is found to be localized over two I atoms and the two atoms are bound by a three-electron hemi bond. The solvation, interaction, and vertical detachment energies are calculated for all I(2) (-).nH(2)O clusters. Energy of interaction and vertical detachment energy profiles show stepwise saturation, indicating geometrical shell closing in the hydrated clusters, but solvation energy profile fails to show such behavior. A linear correlation is observed between the calculated energy of interaction and vertical detachment energy. It is observed that formation of I(2) (-)-water cluster induces significant shifts from the normal O-H stretching modes of isolated H(2)O. However, bending mode of H(2)O remains insensitive to the successive addition of solvent H(2)O units. Weighted average energy profiles and IR spectra are reported for all the hydrated clusters based on the statistical population of individual conformers at room temperature.     

Theoretical studies on photoelectron and IR spectral properties of Br2.-(H2O)n clusters

We report vertical detachment energy (VDE) and IR spectra of Br2.-.(H2O)n clusters (n=1-8) based on first principles electronic structure calculations. Cluster structures and IR spectra are calculated at Becke's half-and-half hybrid exchange-correlation functional (BHHLYP) with a triple split valence basis function, 6-311++G(d,p). VDE for the hydrated clusters is calculated based on second order Moller-Plesset perturbation (MP2) theory with the same set of basis function. On full geometry optimization, it is observed that conformers having interwater hydrogen bonding among solvent water molecules are more stable than the structures having double or single hydrogen bonded structures between the anionic solute, Br2.-, and solvent water molecules. Moreover, a conformer having cyclic interwater hydrogen bonded network is predicted to be more stable for each size hydrated cluster. It is also noticed that up to four solvent H2O units can reside around the solute in a cyclic interwater hydrogen bonded network. The excess electron in these hydrated clusters is localized over the solute atoms. Weighted average VDE is calculated for each size (n) cluster based on statistical population of the conformers at 150 K. A linear relationship is obtained for VDE versus (n+3)(-1/3) and bulk VDE of Br2.- aqueous solution is calculated as 10.01 eV at MP2 level of theory. BHHLYP density functional is seen to make a systematic overestimation in VDE values by approximately 0.5 eV compared to MP2 data in all the hydrated clusters. It is observed that hydration increases VDE of bromine dimer anion system by approximately 6.4 eV. Calculated IR spectra show that the formation of Br2.--water clusters induces large shifts from the normal O-H stretching bands of isolated water keeping bending modes rather insensitive. Hydrated clusters, Br2.-.(H2O)n, show characteristic sharp features of O-H stretching bands of water in the small size clusters.     

A theoretical study on structures, energetics, and spectra of Br-.nCO2 clusters: towards bridging the gap between micro-domain and macro-domain

Structures, energetics, and spectra of Br(-).nCO(2) (n = 1-8) clusters are studied based on ab initio electronic structure theory. The geometry of each size of clusters is evaluated by employing second-order Moller-Plesset (MP2) perturbation theory. It is observed that the solvent CO(2) molecules approach the bromide moiety from one side in an asymmetric fashion except for the Br(-).8CO(2) cluster. Simple electrostatic model for charge-quadrupole interactions is valid for the Br(-).nCO(2) clusters. Reduced variational space based energy decomposition method shows that the electrostatic interaction is the major component and polarization and charge transfer energies are the other significant components of the total interaction energy. Both adiabatic and vertical electron detachment energies and solvation energies are calculated at MP2 level of theory. We have observed an excellent agreement between theory and experiment for the vertical detachment and solvation energies. Calculated quantities based on the analytical expression which connects the finite domain to macroscopic one are found to be very good in agreement with the available experimental results. The present study reveals a 2.6 eV increase in the detachment energy of bromide anion due to the solvation effect of CO(2), which is relatively small compared to that of the corresponding 4.7 eV increase in detachment energy in water.     

Structures of [(CO2)n(CH3OH)m](-) (n = 1-4, m = 1, 2) cluster anions

The infrared photodissociation spectra of [(CO 2) n (CH 3OH) m ] (-) ( n = 1-4, m = 1, 2) are measured in the 2700-3700 cm (-1) range. The observed spectra consist of an intense broad band characteristic of hydrogen-bonded OH stretching vibrations at approximately 3300 cm (-1) and congested vibrational bands around 2900 cm (-1). No photofragment signal is observed for [(CO 2) 1,2(CH 3OH) 1] (-) in the spectral range studied. Ab initio calculations are performed at the MP2/6-311++G** level to obtain structural information such as optimized structures, stabilization energies, and vibrational frequencies of [(CO 2) n (CH 3OH) m ] (-). Comparison between the experimental and the theoretical results reveals the structural properties of [(CO 2) n (CH 3OH) m ] (-): (1) the incorporated CH 3OH interacts directly with either CO 2 (-) or C 2O 4 (-) core by forming an O-HO linkage; (2) the introduction of CH 3OH promotes charge localization in the clusters via the hydrogen-bond formation, resulting in the predominance of CO 2 (-).(CH 3OH) m (CO 2) n-1 isomeric forms over C 2O 4 (-).(CH 3OH) m (CO 2) n-2 ; (3) the hydroxyl group of CH 3OH provides an additional solvation cite for neutral CO 2 molecules.     

Microhydration of NO3(-): a theoretical study on structure, stability and IR spectra

A systematic study on the structure and stability of nitrate anion hydrated clusters, NO3(-) x n H2O (n = 1-8) are carried out by applying first principle electronic structure methods. Several possible initial structures are considered for each size cluster to locate equilibrium geometry by applying a correlated hybrid density functional with 6-311++G(d,p) basis function. Three different types of arrangements, namely, symmetrical double hydrogen bonding, single hydrogen bonding and inter-water hydrogen bonding are obtained in these hydrated clusters. A structure having inter-water hydrogen bonding is more stable compared to other arrangements. Surface structures are predicted to be more stable over interior structures. Up to five solvent H2O molecules can stay around solute NO3(-) anion in structures having an inter-water hydrogen-bonded cyclic network. A linear correlation is obtained for weighted average solvent stabilization energy with the size (n) of the hydrated cluster. Distinctly different shifts of IR bands are observed in these hydrated clusters for different kinds of bonding environments of O-H and N=O stretching modes compared to isolated H2O and NO3(-) anion. Weighted average IR spectra are calculated on the basis of statistical population of individual configurations of each size cluster at 150 K.     

The role of water in synthesised hydrotalcites of formula Mg(x)Zn(6 - x)Cr2(OH)16(CO3) x 4H2O and Ni(x)Co(6 - x)Cr2(OH)16(CO3) x 4H2O--an infrared spectroscopic study

Infrared spectroscopy has been used to characterise synthesised hydrotalcites of formula Mg(x)Zn(6 - x)Cr2(OH)16(CO3) x 4H2O and Ni(x)Co(6 - x)Cr2(OH)16(CO3) x 4H2O. The infrared spectra are conveniently subdivided into spectral features based (a) upon the carbonate anion (b) the hydroxyl units (c) water units. Three carbonate antisymmetric stretching vibrations are observed at around 1358, 1387 and 1482 cm(-1). The 1482 cm(-1) band is attributed to the CO stretching band of carbonate hydrogen bonded to water. Variation of the intensity ratio of the 1358 and 1387 cm(-1) modes is linear and cation dependent. By using the water bending band profile at 1630 cm(-1) four types of water are identified (a) water hydrogen bonded to the interlayer carbonate ion (b) water hydrogen bonded to the hydrotalcite hydroxyl surface (c) coordinated water and (d) interlamellar water. It is proposed that the water is highly structured in the hydrotalcite interlayer as it is hydrogen bonded to both the carbonate anion, adjacent water molecules and the hydroxyl surface.     

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.     

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.     

Microhydration shell structure in Cl2*-.nH2O clusters: A theoretical study

We present the results of a detailed study on structure and electronic properties of hydrated cluster Cl2*-.nH2O (n = 1-7) based on a nonlocal density functional, namely, Becke's [J. Chem. Phys. 98, 1372 (1993)] half and half hybrid exchange-correlation functional with a split valence 6-311++G(d,p) basis function. Geometry optimizations for all the clusters are carried out with various possible initial guess structures without any symmetry restriction. Several minimum energy structures (conformers) are predicted with a small difference in total energy. There is a competition between the binding of solvent H2O units with Cl2*- dimer radical anion directly through ion-molecule interaction and forming interwater hydrogen-bonding network in Cl2*-.nH2O (n > or = 2) hydrated cluster. Structure having interwater H-bonded network is more stable over the structure where H2O units are connected to the solute dimer radical anion Cl2*- rather independently either by single or double H bonding in a particular size (n) of hydrated cluster Cl2*-.nH2O. At the maximum four solvent H2O units reside in interwater H-bonding network present in these hydrated clusters. It is observed that up to six H2O units are independently linked to the anion having four double H bondings and two single H bondings suggesting the primary hydration number of Cl2*- to be 6. In all these clusters, the odd electron is found to be mostly localized over the two Cl atoms and these two atoms are bound by a three-electron hemibond. Calculated interaction (between solute and different water clusters) and vertical detachment energy profiles show saturation at n = 6 in the hydrated cluster Cl2*-.nH2O (n = 1-7). However, calculated solvation energy increases with the increase in number of solvent H2O molecules in the cluster. Interaction energy varies linearly with vertical detachment energy for the hydrated clusters Cl2*-.nH2O (n < or = 6). Calculation of the vibration frequencies show that the formation of Cl2*(-)-water clusters induces significant shifts from the normal stretching modes of isolated water. A clear difference in the pattern of IR spectra is observed in the O-H stretching region of water from hexa- to heptahydrated cluster.     

Electronic excited states of [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm= bis(dimethylphosphine)methane)

We present studies of the resonance Raman and electronic luminescence spectra of the [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm = bis(dimethylphosphine)methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about approximately 300 nm. The resonance Raman spectra confirm the assignment of the 256 nm absorption band to a (1)(dsigma --> psigma) transition, a metal-metal-localized transition, in that nu(Au-Au) and overtones of it are strongly enhanced. A resonance Raman intensity analysis of the spectra associated with the 256 nm absorption band gives the ground-state and excited-state nu(Au-Au) stretching frequencies to be 79 and 165 cm(-1), respectively, and the excited-state Au-Au distance is calculated to decrease by about 0.1 A from the ground-state value of 3.05 A. The approximately 300 nm absorption displays a different enhancement pattern, in that resonance-enhanced Raman bands are observed at 103 and 183 cm(-1) in addition to nu(Au-Au) at 79 cm(-1) The compound exhibits intense, long-lived luminescence (in room-temperature CH(3)CN, for example, tau = 0.70 micros, phi(emission) = 0.037) with a maximum at 550-600 nm that is not very medium-sensitive. We conclude, in agreement with an earlier proposal of Mason (Inorg. Chem. 1989, 28, 4366-4369), that the lowest-energy, luminescent excited state is not (3)(dsigma --> psigma) but instead derives from (3)(d(x2-y2,xy --> psigma) excitations. We compare the Au(I)-Au(I) interaction shown in the various transitions of the [Au(2)(dmpm)(3)](ClO(4))(2) tribridged compound with previous results for solvent or counterion exciplexes of [Au(2)(dcpm)(2)](2+) salts (J. Am. Chem. Soc. 1999, 121, 4799-4803; Angew. Chem. 1999, 38, 2783-2785; Chem. Eur. J. 2001, 7, 4656-4664) and for planar, mononuclear Au(I) triphosphine complexes. It is proposed that the luminescent state in all of these cases is very similar in electronic nature.     

Electronic sputtering produced by fission fragments on condensed CO and CO2

Condensed CO and CO2 are bombarded by approximately 65 MeV 252Cf fission fragments and the desorbed ions are analyzed by time-of-flight mass spectrometry as a function of target temperature, in the ranges 25-33 K and 75-91 K, respectively. Absolute desorption yields are measured up to complete ice sublimation. The mass spectra of both ice targets reveal the emission of: (1) low mass ions, produced by direct Coulomb interaction of the highly charged projectiles and delta-electrons with CO and CO2, and (2) pronounced series of cluster ions. The basic ice cluster structures (CO)n and (CO2)n are present in the emitted cluster series such as (CO)nCO+, (CO2)nCO2+, or (CO2)nCO3-. In the case of CO ice, however, the intense production of the series Cn+, Cn-, and (CO)mCn+ shows that Cn is the main cluster structure, consequence of a higher concentration of free carbon atoms in the nuclear track plasma of CO ice than in that of CO2 ice. Ion cluster abundance is observed to decrease exponentially with cluster mass. The decay constant is k(n) congruent with 0.13, about the same for series based on (CO)n and (CO2)n, but a factor 3.3 higher for the Cn series. The Cn clusters are formed by gas-phase condensation, but the (CO)n and (CO2)n clusters are produced by fracturing of the highly excited solid around the nuclear track. A dramatic reduction of the ion desorption yield is observed near T = 29 K for CO and near T = 85 K for CO2, when fast sublimation occurs and ice thickness vanishes. Close to sublimation temperature, the decay constant of the (CO)2Cn+ series increases due to a decreasing formation probability of large Cn clusters.     

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.     

Infrared spectra of O2- x (CO2)n clusters (n=1-6): asymmetric docking at the pi* orbital

Isolated superoxide ions solvated by CO2 have been studied by infrared photodissociation spectroscopy and density-functional theory, using CO2 evaporation upon infrared excitation of the O2- x (CO2)n (n=1-6) parent ions. We can assign the observed frequencies to the asymmetric stretch vibration and its combination bands with the symmetric stretch and the overtone of the bending vibration of CO2 in various binding situations. We interpret our findings with the help of density-functional theory. Our data suggest that only one CO2 moiety binds strongly to the O2-, whereas the rest of the CO2 molecules are weakly bound, which is consistent with the experimental spectra. The lobes of the pi* orbital of O2- provide a template for the structure of the microsolvation environment.     

Infrared spectroscopy of water cluster anions, (H2O)n=3-24-)in the HOH bending region: persistence of the double H-bond acceptor (AA) water molecule in the excess electron binding site of the class I isomers

We report vibrational predissociation spectra of water cluster anions, (H(2)O)(n=)()(3)(-)(24)(-) in the HOH bending region to explore whether the characteristic red-shifted feature associated with electron binding onto a double H-bond acceptor (AA) water molecule survives into the intermediate cluster size regime. The spectra of the "tagged" (H(2)O)(n)()(-).Ar clusters indeed exhibit the signature AA band, but assignment of this motif to a particular isomer is complicated by the fact that argon attachment produces significant population of three isomeric forms (as evidenced by their photoelectron spectra). We therefore also investigated the bare clusters since they can be prepared exclusively in the high binding (isomer class I) form. Because the energy required to dissociate a water molecule from the bare complexes is much larger than the transition energies in the bending region, the resulting (linear) action spectroscopy selectively explores the properties of clusters with most internal energy content. The (H(2)O)(15)(-) predissociation spectrum obtained under these conditions displays a more intense AA feature than was found in the spectra of the Ar tagged species. This observation implies that not only is the AA motif present in the class I isomer, but also that it persists when the clusters contain considerable internal energy.     

Raman,infrared and force field studies of K2(12)C2O4 x H2O and K2(13)C2O4 x H2O in the solid state and in aqueous solution,and of (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O in the solid state

The Raman and infrared spectra of solid K2(12)C2O4 x H2O are reported together with, for the first time, the corresponding Raman and infrared spectra of solid K2(13)C2O4 x H2O. Raman spectra of aqueous solutions of both isotopomers are also reported. In the solid state the oxalate anion is planar with D2h symmetry in this salt, whereas in aqueous solution the Raman spectra of the anion are best interpreted on the basis of D2d symmetry. The Raman spectra of solid (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O, in which the oxalate anion is twisted from planarity by 28 degrees about the CC bond, have also been recorded. Several reassignments have been made. The harmonic force field for the oxalate anion in the D2h, D2 and D2d geometries has been determined in part, and approximate values of key valence force constants determined. All the observed band wavenumbers and 12C/13C isotopic shifts are well reproduced by the force fields. The potential energy distribution of the totally symmetric normal modes of planar oxalate indicates that each mode consists of extensively mixed symmetry corrdinates and that the labels previously used for the bands seen here at 475 and 879 cm(-1) would better be described as v(CC) and deltaS(CO2), respectively, putting them in the same wavenumber order as v(NN) and deltaS(NO2) for the isoelectronic and isostructural molecule N2O4. The stretching force constants of N2O4 and planar C2O4(2-) are established to be in the order f(NN) < f(CC) and f(NO) > f(CO), consistent with the known relative bond lengths.     

Raman and infrared spectroscopic study of the anhydrous carbonate minerals shortite and barytocalcite

The Raman spectra of shortite and barytocalcite complimented with infrared spectra have been used to characterise the structure of these carbonate minerals. The Raman spectrum of barytocalcite shows a single band at 1086cm(-1) attributed to the (CO(3))(2-) symmetric stretching mode, in contrast to shortite where two bands are observed. The observation of two bands for shortite confirms the concept of more than one crystallographically distinct carbonate unit in the unit cell. Multiple bands are observed for the antisymmetric stretching and bending region for these minerals proving that the carbonate unit is distorted in the structure of both shortite and barytocalcite.     

An infrared investigation of the (CO2)n- clusters: core ion switching from both the ion and solvent perspectives

The (CO2)n- clusters are thought to accommodate the excess electron by forming a localized molecular anion, or "core ion", solvated by the remaining, largely neutral CO2 molecules. Earlier studies interpreted discontinuities in the (CO2)n- photoelectron spectra to indicate that both the CO2- and C2O4- species were present in a size-dependent fashion. Here we use vibrational predissociation spectroscopy to unambiguously establish the molecular structures of the core ions in the 2 < or = n < or = 17 size range. Spectra are reported in the 2300-3800 cm(-1) region, which allows us to independently monitor the contribution of each ion through its characteristic overtone and combination bands. These signature bands are observed to be essentially intact in the larger clusters, establishing that the CO2- and C2O4- molecular ions are indeed the only electron accommodation modes at play. The size dependence of the core ion suggested in earlier analyses of the photoelectron spectra is largely confirmed, although both species are present over a range of clusters near the expected critical cluster sizes, as opposed to the prompt changes inferred earlier. Perturbations in the bands associated with the nominally neutral CO2 "solvent" molecules are correlated with the changes in the molecular structure of the core ion. These observations are discussed in the context of a diabatic model for electron delocalization over the CO2 dimer. In this picture, the driving force leading to the transient formation of the monomer ion is traced to the solvent asymmetry inherent in an incomplete coordination shell.     

Dynamics of charge-transfer-to-solvent precursor states in I- (water)n (n = 3-10) clusters studied with photoelectron imaging

The dynamics of charge-transfer-to-solvent states are studied in I- (H2O)(n=3-10) clusters and their deuterated counterparts using time-resolved photoelectron imaging. The photoelectron spectra for clusters with n > or = 5 reveal multiple time scales for dynamics after their electronic excitation. An increase in the vertical detachment energy (VDE) by several hundred millielectronvolts on a time scale of approximately 1 ps is attributed to stabilization of the excess electron, primarily through rearrangement of the solvent molecules, but a contribution to this stabilization from motion of the I atom cannot be ruled out. The VDE drops by approximately 50 meV on a time scale of tens of picoseconds; this is attributed to loss of the neutral iodine atom. Finally, the pump-probe signal decays with a time constant of 60 ps-3 ns, increasing with cluster size. This decay is commensurate with the growth of very slow electrons and is attributed to autodetachment. Smaller clusters (n = 3, 4) display simpler dynamics. Anisotropy parameters are reported for clusters n = 4-9.     

Structure and dynamics of the solvated electron in alcohols from resonance Raman spectroscopy

Resonance Raman (RR) spectroscopy is used to probe the structure and excited-state dynamics of the solvated electron in the primary liquid alcohols methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), and n-butanol (n-BuOH). The strong resonance enhancements (>or=10(4) relative to pure solvent) of the libration, CO stretch, COH bend, CH3 bend, CH2 bend, and OH stretch reveal significant Franck-Condon coupling of the intermolecular and intramolecular vibrational modes of the solvent to the electronic excitation of the solvated electron. All enhanced bands are fully accounted for by a model of the solvated electron that is comprised of several nearby solvent molecules that are only perturbed by the presence of the electron; no new molecular species are required to explain our data. The 340 cm(-1) downshift observed for the OH stretch frequency of e-(MeOH), relative to pure solvent, strongly suggests that the methanol molecules in the first solvent shell have the hydroxyl group directed linearly toward the excess electron density. The smaller downshifts observed for e-(EtOH), e-(n-PrOH), and e-(n-BuOH) are explained in terms of a OH group that is bent 28-40 degrees from linear. The Raman cross sections and absorption spectra are modeled, lending quantitative support for the inhomogeneous origin of the broad absorption spectra, the necessity of OH local motion in all enhanced Raman modes of the alcohols, and the dominant librational response of the solvent upon photoexcitation of the electron.     

Temperature-induced structural changes in glassy, supercooled, and molten silica from 77 to 2150 K

In situ polarized and depolarized Raman spectra of glassy, supercooled, and molten SiO2 have been measured over the broad temperature range 77-2150 K in an effort to examine possible structural changes caused by temperature variation. A new experimental setup using a CO2 laser for heating the sample has been designed allowing measurement with controllable blackbody radiation background at temperatures up to 2200 K. Careful and systematic relative intensity measurements and the use of the isotropic and anisotropic Raman representation of the spectra revealed hidden bands in the bending mode region and resolved bands in the stretching region of the spectra. Overall the spectra behavior shows similarities with the spectra of the recently studied tetrahedral glasses/melts of ZnCl2 and ZnBr2. Increasing temperature causes subtle changes of the relative intensities within the silicon-oxygen stretching region at approximately 750-850 cm(-1) and gives rise to a new band at approximately 930 cm(-1). The spectral behavior is interpreted to indicate that the "SiO42" tetrahedra are bound to each other to form the network by apex-bridging and partly by edge-bridging oxygens. The network structure of the glass/melt is formed by mixing a variety of tetrahedra participating in "open" (cristobalitelike), "cluster" (supertetrahedra), and "chain" edge-bridged substructures bound to each other by bridging oxygens. A weak in intensity but strongly polarized composite band is resolved at approximately 1400 cm(-1) and is assigned to Si[Double Bond]O terminal bond frequency. Temperature rise increases the concentration of the terminal bonds by breaking up the network. These structural changes are reminiscent of the polyamorphic transformations occurring in silica as has recently been predicted by computer simulations. At low frequencies the Raman spectra reveal the presence of the Boson peak at approximately 60 cm(-1) which is well resolved even above melting temperature up to 2150 K.