Vibrational analysis study of aluminum trifluoride phases

The vibrational modes of three solid AlF3 phases (alpha, beta, and amorphous high surface area AlF3) are investigated. Calculations have been performed using hybrid exchange correlation functionals to determine the equilibrium geometries and Gamma-point phonon frequencies for the alpha-AlF3 and beta-AlF3 phases. The calculated optical modes are in excellent agreement with experiment. The IR absorption of the amorphous, glasslike high surface area (HS)-AlF3 is also discussed. Deconvolution of the broad envelope of IR stretches and bending vibrations identifies the components of the observed broad band. From the IR vibrational spectrum it has been shown that both short-range and medium-range disorder are present within HS-AlF3. Structural phase transitions are identified by their phase transition temperature Tc, measured by thermal analysis.     

Symmetry properties of vibrational modes in mesoporphyrin IX dimethyl ester investigated by polarization-sensitive resonance Raman and CARS spectroscopy

The symmetry properties of selected vibrational modes of mesoporphyrin IX dimethyl ester (MP-IX-DME) in solution are investigated under different electronic resonance conditions. The Raman band parameters of the macrocycle modes nu(2), nu(10), nu(11), and nu(19) are determined from a quantitative analysis of polarized spontaneous resonance Raman (RR) and polarization-sensitive (PS) multiplex coherent anti-Stokes Raman scattering (CARS) spectra obtained with pre-resonant B band and resonant Qx band excitation, respectively. Additionally, the molecular geometry and the vibrational modes of MP-IX-DME are calculated by employing density functional theory (DFT) on the B3LYP/6-31G(d) level. Both the DFT-derived structure and the Raman spectroscopic parameters of MP-IX-DME indicate minor deviations from an ideal D2h macrocycle symmetry. To assess the influence of the beta substitution pattern on the in-plane symmetry, calculated normal-mode vectors and several experimentally detected parameters, such as peak positions, depolarization ratios, and coherent phases, are analyzed. The effects of the macrocycle substitution pattern are different for the selected vibrational modes: nu(2) in particular is very sensitive to subtle perturbations of the in-plane symmetry. The considerable activity of totally symmetric vibrations observed in the PS CARS spectra of MP-IX-DME and the correlation of mode symmetries with coherent phases confirm earlier PS CARS results on octaethylporphine (OEP) acquired under the same electronic resonance conditions.     

On the role of coupling in mode selective excitation using ultrafast pulse shaping in stimulated Raman spectroscopy

The coherence of two coupled two-level systems, representing vibrational modes in a semiclassical model, is calculated in weak and strong fields for various coupling schemes and for different relative phases between initial state amplitudes. A relative phase equal to pi projects the system into a dark state. The selective excitation of one of the two, two-level systems is studied as a function of coupling strength and initial phases.     

Vibrational properties of the compressed and the relaxed 1,4,5,8-naphthalene-tetracarboxylic dianhydride monolayer on Ag(111)

Layers of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) grown on Ag(111) at about 80 K have been investigated using Fourier transform infrared spectroscopy, spot profile analysis low-energy electron diffraction, and temperature programmed desorption. Specifically, the compressed and the relaxed monolayer, as well as the transformation between the two ordered phases have been analyzed in detail. It is found that the two monolayer phases display distinctly different vibrational spectra and can thus be discriminated with high accuracy and sensitivity. For the NTCDA/Ag(111) monolayer strong in-plane vibrational modes point at a marked dynamic charge transfer between molecule and metal substrate and provide clear evidence for an efficient electronic coupling to the Ag(111) surface in conjunction with a partially filled electronic level at the Fermi energy. The bilayer, on the other hand, is largely electronically decoupled from the substrate and, according to the vanishing infrared-active in-plane vibrational modes, is oriented parallel to the surface. On the basis of spectroscopic data the metastable nature of the bilayer phase is identified as such, leading to an improved understanding of processes encountered in the course of layer preparation and resolving inconsistencies reported in the literature.     

DFT Calculations of the Molecular Force Field of Vanadyl Nitrate,VO(NO3)3

A structural and vibrational theoretical study for vanadyl nitrate was carried out. The Density Functional Theory (DFT) has been used to study vibrational properties. The structures were fully optimized at the B3LYP/6‐31G*, B3LYP/6‐311G*, and B3LYP/6‐311+G* levels of theory and the harmonic vibrational frequencies were evaluated at the same level. The calculated harmonic vibrational frequencies for vanadyl nitrate are consistent with their experimental IR and Raman spectra in gas and liquid phases. Through these calculations a precise knowledge of the normal modes of vibration was obtained, considering the coordination mode adopted by the nitrate group in the mirror plane as monodentate and bidentate. A total assignment of the observed bands in the vibrational spectra for vanadyl nitrate is proposed in this work. The nature of the V–O and V ← O bonds in the compound was systematically and quantitatively investigated by means of the Natural Bond Order (NBO) analysis. The topological properties of the electronic charge density were analyzed employing Bader's Atoms in Molecules theory (AIM).     

Theoretical study of the syn- and anti-conformers of 2,2ʹ-bifuran derivatives: rotational barrier and solvent effect

The optimised molecular structures, vibrational wavenumbers and corresponding vibrational assignments of the syn- and anti-conformers of 2,2?-bifuran and its nitro, fluoro, methyl and hydroxyl derivatives were obtained using density functional theory. The starting structures with C₂ symmetry of all the ground state structures were considered and the transition state arising from syn-anti isomerisation was also modelled. All structures were fully optimised, and the geometries, dipole moments, charge, thermodynamic properties, and energies are reported. The calculated vibrational wavenumbers were assigned to the various fundamental modes of vibrations. The integral Equation Formalism Polarisation Continuum Model (IEF-PCM) was used to calculate the optimised geometry and the vibrational wavenumbers for all the compounds in different solvents. The results indicate that in the gas phase, the syn-conformer is more stable while in solution phases the conformational preference depends on the polarity of the solvent.     

Vibrational solvatochromism and electrochromism of infrared probe molecules containing C≡O, C≡N, C=O, or C-F vibrational chromophore

Solvatochromic vibrational frequency shifts of a few different infrared (IR) probe molecules have been studied by carrying out quantum chemistry calculations for a number of their water clusters. We are particularly focused on the vibrational solvatochromic and electrochromic effects on the CO, CN, and CF stretch modes in carbon monoxide, acetone, 4-cyanopyridine, p-tolunitrile, fluorobenzene, and 3-fluoropyridine. Using multiple interaction site antenna model, we show that their solvatochromic vibrational frequency shifts can be successfully described by considering spatially nonuniform electrostatic potential generated by the surrounding water molecules. It turns out that the CO and CF stretch mode frequencies are approximately proportional to the solvent electric field projected onto the bond axes, whereas the vibrational frequencies of the nitrile stretch mode in 4-cyanopyridine and p-tolunitrile are not. Consequently, it is confirmed that the vibrational Stark tuning rates of the CO and CF stretching modes can be directly used to describe their solvatochromic frequency shifts in condensed phases. However, the nitrile stretch mode frequency shift induced by solvent electrostatic potential appears to be more complicated than its electrochromic phenomenon. To examine the validity of the distributed interaction site model for solvatochromic frequency shifts of these vibrational chromophores, we thus calculated the vibrational Stark tuning rates of the CO, CN, and CF stretch modes and found that they are in good agreement with the experimental results found in literatures. This confirms that a collection of properly chosen distributed interaction sites can be an excellent electric antenna sensing local electrostatics that affects on vibrational frequencies of IR probe modes.     

The structure and vibrational spectra of some ferroelectric and ferroelastic alkylammonium halogenoantimonates(III) and bismuthates(III)

Crystals from the rich family of alkylammonium halogenoantimonates(III) and bismuthates(III) containing small bioctahedra as well as infinite two- or one-dimensional polyoctahedral units attract particular attention from the point of view of possible applications. Such crystals exhibit a wealth of phase transitions including those to ferroelectric and ferroelastic phases. The analysis of vibrational spectra performed in this paper with respect to modes assigned to alkylammonium group shows that their interactions with polyanionic sublattice is of medium strength. The absorption pattern and particularly the splitting of bands on cooling very well correlates with other anomalies of physical properties and particularly with the behaviour of second moment of PMR lines and T₁ and T_1ρ relaxation times as functions of temperature. The temperature behaviour of modes is well described in terms of pseudospin–phonon coupling model that we presented for different modes in various crystals. The role of anionic dynamics is not sufficiently recognised but in one case, namely for the low temperature transition in (MA)₃Bi₂Br₉ crystal this role is predominant, according to vibrational and NQR spectra of methylammonium and isostructural caesium salt.     

Comparative study of infrared and Raman spectra of CCl4 in vapour and condensed phases: effect of LO-TO splitting resulting from hetero-isotopic TD-TD interactions

Salient features of an in-depth comparative study of infrared and Raman spectra of CCl(4) in vapour, liquid and condensed phases are presented. Wavenumbers of nu(4), nu(1)+nu(4), nu(3) and 2 nu(3) modes of CCl(4) vapour in infrared and Raman spectra are found to be in good agreement. Analysis of the vibrational spectra of liquid CCl(4) together with the spectroscopic observations on solid CCl(4) at low temperatures reveal TD-TD interaction amongst various CCl(4) isotopes in condensed states. The concept of LO-TO splitting of dipole active nu(3) and nu(1)+nu(4) Fermi doublet have been invoked to explain several features of the vibrational spectra of liquid CCl(4). There is significant strengthening of Fermi resonance interaction between nu(3) and nu(1)+nu(4) modes of CCl(4) in condensed phases relative to that in vapour phase. The Fermi resonance interaction parameter W has been found to be independent of molecular environment.     

Lattice vibrations of manganese oxides. Part I. Periodic structures

Raman scattering (RS) and Fourier transform-infrared (FT-IR) spectroscopy have been applied to the structural characterisation of manganese dioxides (MDOs). A variety of synthetic battery-grade MDOs are investigated for comparison to the natural phases. The RS and FT-IR spectra are analysed on the basis of the local environment in the MDO structures considering the vibrations of the MnO6 octahedral building the lattices. The vibrational modes of the MnO6 units expand over 400-650 cm(-l) with additional bands in the low-wavelength region. Structural trends are deduced from the comparison of the vibrational spectra of the MDO phases investigated: birnessite, bixbyite, coronadite, groutite, hausmannite, hollandite, manganosite, pyrolusite, ramsdellite, romanechite, spinel, and todorokite.     

Importance of accurate spectral simulations for the analysis of terahertz spectra: citric acid anhydrate and monohydrate

The terahertz (THz) spectra of crystalline solids are typically uniquely sensitive to the molecular packing configurations, allowing for the detection of polymorphs and hydrates by THz spectroscopic techniques. It is possible, however, that coincident absorptions may be observed between related crystal forms, in which case careful assessment of the lattice vibrations of each system must be performed. Presented here is a THz spectroscopic investigation of citric acid in its anhydrous and monohydrate phases. Remarkably similar features were observed in the THz spectra of both systems, requiring the accurate calculation of the low-frequency vibrational modes by solid-state density functional theory to determine the origins of these spectral features. The results of the simulations demonstrate the necessity of reliable and rigorous methods for THz vibrational modes to ensure the proper evaluation of the THz spectra of molecular solids.     

Recognition of the syndiotactic polypropylene polymorphs via dynamic-mechanical analysis

Three syndiotactic polypropylene samples were crystallized under different conditions in order to obtain different polymorphs. A first sample was crystallized at high temperature, obtaining the helical form I; a second was crystallized from the melt at 0°C for many days obtaining the trans-planar mesophase; a third sample was obtained by solvent induced crystallization followed by annaeling of the trans-planar mesophase, leading to a mixture of both the helical forms I and II. In the dynamic-mechanical analysis the helical form I showed only one peak of tan δ corresponding to the amorphous glass transition. The other polymorphs also showed this transition centered at about the same temperature. Beside the peak corresponding to the Tg, the trans-planar mesophase was characterized by a peak appearing at 70°C, and the helical form II by a peak at 100°C. These peaks, unambiguously associated to transitions of the different forms, can be considered a distinctive evidence for the polymorphs obtained in different processing conditions.     

Polymorphism of crystalline alpha-quaterthiophene and alpha-sexithiophene: ab initio analysis and comparison with inelastic neutron scattering response

Phonons in the alpha-quaterthiophene (4T) and alpha-sexithiophene (6T) polymorph phases are investigated using the direct method combined with density functional theory (DFT)-based total energy calculations. The simulation of inelastic neutron scattering spectra (INS) on the LT and HT polymorph phases of 4T and 6T enable the corresponding spectral signatures of these materials to be identified. In particular, there are two fingerprints: (i) the low-frequency vibrational modes (frequencies lower than 200 cm(-1)) and (ii) the vibrational modes in the 600-900 cm(-1) frequency range. The good agreement with the INS experimental data allows us to assign unambiguously the origin of all features (first-order and high-order processes) of these spectra and to predict that the LT phase is the phase measured experimentally both on the 4T and 6T materials. Moreover, the broad background in the 600-1400 cm(-1) frequency range and the well-defined features which appear around 940 cm(-1) in the calculated INS spectra of 4T/HT and 6T/HT are assigned to multiphonon contributions. This multiphonon contribution at 940 cm(-1), which is absent in the 4T/LT and 6T/LT INS spectra, also constitutes a fingerprint of the HT phases. Finally, the calculated dispersion curves of the two polymorph phases of 4T and 6T are given.     

DFT calculation of the chromyl nitrate, CrO2(NO3)2 The molecular force field

We have carried out a structural and vibrational theoretical study for chromyl nitrate. The density functional theory has been used to study its structure and vibrational properties. The geometries were fully optimised at the B3LYP/Lanl2DZ, B3LYP/6-31G* and B3LYP/6-311++G levels of theory and the harmonic vibrational frequencies were evaluated at the same levels. The calculated harmonic vibrational frequencies for chromyl nitrate are consistent with the experimental IR and Raman spectra in the solid and liquid phases. These calculations gave us a precise knowledge of the normal modes of vibration taking into account the type of coordination adopted by nitrate groups of this compound as monodentate and bidentate. We have also made the assignment of all the observed bands in the vibrational spectra for chromyl nitrate. The nature of the Cr-O and Cr<--O bonds in the compound were quantitatively investigated by means of Natural Bond Order (NBO) analysis. The topological properties of electronic charge density are analysed employing Bader's Atoms in Molecules theory (AIM).     

Laser raman spectra of the stable low-temperature phase of ferrocene

Laser Raman spectra of ferrocene crystal are recorded for the stable (orthorhombic) and metastable (triclinic) low-temperature phases, and the stable and undercooled (monoclinic) high-temperature phases.The skeletal vibrational modes [v₄(A_1g) and v₁₆(E_1g)], the CH bending (⊥e) mode [v₂₅(E_2g)], and the lattice modes below 100 cm^?1 show characteristic changes among these phases.     

Anharmonic C?H and C=O Interactions in Peptide and Sugar

C?H and C=O stretching modes are two among many structural and dynamic probes of proteins and peptides in condensed phases. Anharmonic properties of these two modes in peptide and sugar have been examined using a second-order perturbative vibrational approach. High order force constants were obtained and examined to ˉnd how crucial they are in determining the degree of mode localization and the nature of mode anharmonicity of the two stretching modes. It is found that the C?H mode is highly localized,and its diagonal anharmonicity is mainly determined by the mode itself. However, the C=O mode is largely delocalized, and the diagonal anharmonicity involves contributions from other modes. The o?-diagonal anharmonicity between C?D and C=O modes is found to be negative in deuterated species, di?ering from those of the non-deuterated ones. It is also found that inter-mode interaction between each of the two modes with low-frequency modes contribute signiˉcantly to the o?-diagonal anharmonicity. These low-frequency modes give rise to a network of energy relaxation or intramolecular vibrational energy redistribution pathways which can be used to examine temporal behavior of intramolecular vibration energy °ow, provided a femtosecond broadband two-dimensional infrared spectroscopy is available.     

Vibrational energy redistribution in jet-cooled hydrogen-bonded phenols

Dispersed fluorescence spectra of jet-cooled hydrogen-bonded phenols have been observed by excitation of intra- and inter-molecular vibrational levels. The spectra show that vibrational energy redistribution occurs from the excited vibronic level into intermolecular vibrational modes. Energy redistribution within the intermolecular vibrational modes was also found.     

Intramolecular vibrational coupling contribution to temperature dependence of vibrational mode frequencies

High-frequency vibrational modes in molecules in solution are sensitive to temperature and shift either to lower or higher frequencies with the temperature increase. These frequency shifts are often attributed to specific interactions of the molecule and to the solvent polarization effect. We found that a substantial and often dominant contribution to sensitivity of vibrational high-frequency modes to temperature originates from anharmonic interactions with other modes in the molecule. The temperature dependencies were measured for several modes in ortho-, meta-, and para-isomers of acetylbenzonitrile in solution and in a solid matrix and compared to the theoretical predictions originated from the intramolecular vibrational coupling (IVC) evaluated using anharmonic density functional theory calculations. It is found that the IVC contribution is essential for temperature dependencies of all high-frequency vibrational modes and is dominant for many modes. As such, the IVC contribution alone permits predicting the main trend in the temperature dependencies, especially for vibrational modes with smaller transition dipoles. In addition, an Onsager reaction field theory was used to describe the solvent contribution to the temperature dependencies.     

Vibrational projection analysis: New tool for quantitatively comparing vibrational normal modes of similar molecules

A new method for quantitatively comparing calculated vibrational modes is described that relies on projecting the vectors describing the normal modes of one molecule onto those of a basis molecule. The procedure virtually automates the assignment of vibrational modes from one molecule to a second, structurally similar one. We illustrate the concept by using the classical Wilson modes of benzene as a basis for describing normal modes of the monosubstituted benzene derivatives phenol, phenol-d5, and phenol radical cation. These examples demonstrate the method's power for accurately assigning and comparing the normal modes of molecules perturbed by chemical substitution, isotopic substitution, or oxidation state. The vibrational projection analysis method—a special case of vector projection analysis—is compared and contrasted with total energy distribution analysis, perhaps the most commonly used technique for quantitatively comparing vibrational modes, and is found superior in each case when comparing normal modes. Vibrational projection analysis need not be limited to single molecules and quantum calculations, because normal modes may be obtained for much larger systems using molecular mechanics or molecular dynamics techniques. The method should therefore prove useful for interpreting the normal modes of ordered periodic solids and structures perturbed by noncovalent contacts, including proteins and polymers. The method may also prove useful in evaluating new computational methods by allowing direct, quantitative comparison of the vibrational modes obtained from different techniques. The power of this technique will make vibrational projection analysis a valuable tool for computational chemists as well as those using calculations to complement vibrational spectroscopic measurements. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1663–1674, 1998     

Electronic and vibrational spectra of Mn rich sursassite

The optical spectrum of Mn2+ in octahedral coordination for sursassite is characterized by well resolved bands at 580, 515, 470, 390, 340, and 295 nm (17240, 19420, 21280, 25640, 29410 and 33900 cm-1). Crystal field parameters evaluated from the observed bands are Dq=690, B=680 and C=2800 cm-1. A broad band centred around 13000 cm-1 attributed to Fe(III) ion is an impurity in sursassite confirmed from EDX analysis. Vibrational spectra have been investigated both by IR and Raman spectroscopy. The correlation between vibrational modes and the structural properties of the manganese silicate, sursassite, is made and compared with other silicates. Two vibrational modes of CO(3)2- observed; the antisymmetric stretching mode (nu3) at 1420 cm-1 (IR active) and the out-of-plane bending mode (nu2) (IR and Raman active) at approximately 875 cm-1. This confirms the Mn rich phases in sursassite as observed from SEM probably an Mn carbonate-rhodochrosite.