Vibrational spectra, normal coordinate analysis and thermodynamics of 2, 5-difluorobenzonitrile

The FTIR spectrum of 2, 5-difluorobenzonitrile has been recorded in the region 200–4000 cm⁻¹ (in liquid phase). The laser Raman spectrum in the range of 0–3500 cm⁻¹ (in liquid phase) has also been recorded. The spectra have been analyzed assuming C _s point group symmetry for the molecule. A zero-order normal coordinate analysis has been made for the molecule using force constants derived earlier. On the basis of potential energy distributions and eigen vectors unambiguous vibrational assignments have been made for all the fundamentals of the molecule. Thermodynamic functions have also been computed in the temperature range 200–1000 K by utilizing the observed fundamental frequencies assuming rigid-rotor harmonic oscillator approximation.     

Infrared spectra of brassinolide and castasterone steroid phytohormones and their 24-epi derivatives

Absorption bands in IR spectra of brassinolide, castasterone, and their 24-epi derivatives in the frequency range 3800–1000 cm^–1 have been interpreted. A number of spectral features distinguishing brassinolide from castasterone have been found. The conducted analysis shows that the structural differences manifest themselves in IR spectra of the investigated brassinosteroids in the region of stretching vibrations of CO–H, C=O, C–OH, C–O–C, CH₃, CH₂, and CH groups. The main distinctions in IR spectra of brassinolides and castasterones are due to the B ring structure.     

Laser Raman and infra-red spectra of biomolecule: 5-aminouracil

Laser Raman (200–4000 cm⁻¹) and IR (200–4000 cm⁻¹) spectra of 5-aminouracil were recorded in the region 200–4000 cm⁻¹. Assuming a planar geometry and C_s point group symmetry, it has been possible to assign all the 36 (25a′ + 11a″) normal modes of vibration for the first time. The two NH bonds of the NH₂ group appear to be equivalent as the NH₂ stretching frequencies satisfy the empirical relation proposed for the two equivalent NH bonds of the NH₂ group. The two NH₂ stretching frequencies are distinctly separated from the CH/NH ring stretching frequencies. A strong and sharp IR band at 3360 cm⁻¹ could be identified as the anti-symmetric NH₂ mode whereas the band at 3290 cm⁻¹ with smaller density could be identified as the symmetric NH₂ stretching mode. All other bands have also been assigned different fundamentals/overtones/combinations.      

Theoretical interpretation of spectral signs of an oxymethyl group in the IR spectrum of methyl-β-D-glucopyranoside

For the first time, we have assigned the observed absorption bands and interpreted the IR spectrum of methyl-β-D-glucopyranoside in detail in the 1500–800 cm⁻¹ region, based on a full calculation of the frequencies and absolute intensities of the normal vibrations of the molecule and their comparison with the experimental data. We have identified two groups of spectral signs indicating an oxymethyl substituent has replaced the hydroxyl group on the C₍₁₎ atom in the glucopyranoside: absorption bands of medium intensity due to the characteristic vibrations of the substituent, and intense bands due to an unusual “interaction” between many structural moieties. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 721–727, November–December, 2006.     

Calculation of the structure and IR spectrum of hydrogen-bonded methyl-β-D-glucopyranoside by the density-functional method

The IR spectrum and structure of methyl-β-D-glucopyranoside have been studied theoretically taking into account the influence on them of the hydrogen bond formed in the sample. Density-functional theory with the B3LYP functional in basis 6-31G(d) was used to minimize the energies and calculate the structures, electro-optical parameters, force constants, frequencies of normal harmonic vibrations, and intensities in IR spectra of the simplest H-bonded dimeric complexes of methyl-β-D-glucopyranoside. The calculated spectra of H-bonded complexes were compared with those of the free molecule and the experimental spectrum in the range 400–3700 cm^–1. Conclusions about the structure of methyl-β-D-glucopyranoside were made. The interpretation of its IR spectrum was refined.     

Optical and IR studies on r.f. magnetron sputtered ultra-thin MoO3 films

Ultra-thin MoO₃ films were deposited onto glass and Si substrates by r.f. magnetron sputtering. The optical and IR properties of the films were studied in the range of 250 to 1000 nm and 400 to 1500 cm⁻¹, respectively. The optical transmission spectra show a significant shift in absorption edge. The energy gap of the films deposited at 373 K and 0.1 mbar was found to be 3.93 eV, and it decreases with increasing substrate temperature and decreasing sputtering pressure. The IR transmittance spectra shows strong modes of vibrations of Mo=O and Mo–O–Mo units of MoO₃ molecule. A significant change in energy gap and a shift in frequency of IR modes were observed in ultra-thin MoO₃ films.     

Structure of water-in-oil microemulsions of AOT by infrared spectroscopy

Summary The structure of water in water/AOT/n-heptane reverse micelles has been studied as a function of the [H₂O]/[AOT] ratio (W) by using the absorption IR due to O−H stretching modes in the 3800–3000 cm⁻¹ range. The results show that the IR spectra can be expressed as a sum of contributions from bound- and bulk-like water. The fraction of water in the two ?regions? within the water pool was evaluated as a function ofW. The ?bound? water region seems to hold 3.5 water molecules (corresponding to 7 O−H oscillators) per AOT molecule and its formation is nearly complete atW>6. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

IR spectra of stigmastane series brassinosteroids differing in configuration and number of diol groups

IR spectra of steroid phytohormones of the stigmastane series (22R, 23R)-28-homocastasterone and (22R,23R)-28-homosecasterol and their isomers (22S,23S)-28-homocastasterone and (22S,23S)-28-homosecasterol have been analyzed. The 28-homocastasterone molecule contains diol groups in ring A and in the side chain whereas that of 28-homosecasterol has one diol group in the side chain. The lack of two OH groups in ring A of homosecasterol compared to homocastasterone results in the appearance of stretching vibrational bands of H–C= (ν_max = 3025 cm^–1) and –C=C (ν_max = 1656 cm^–1) groups of ring A. Substantial changes are observed in the area of OH stretching vibrations. Homocastasterones pressed in KBr possess twice as many OH groups as homosecasterols such that absorption band total intensities in IR spectra of both isomers caused by H-bonds of the diol groups in the side chain amount to 65% whereas the share of the 2α,3α group is only 35% of the total intensity. Hence the contribution from the side-chain OH groups of the studied brassinosteroids to the integral optical density of the bands exceeds that from the ring-A OH groups. In dilute CHCl3 solutions of the brassinosteroids, the conformations of the brassinosteroid side chains are not the same. As a result, intramolecular H-bonds of different energy are created. The optical density D_max in band maxima of free OH groups for homocastasterones is three times higher than that for the corresponding band maxima of homosecasterol. This implies that D_max for bands of free OH groups of the homocastasterone ring-A diol group is greater, in contrast with the relatively greater D_max for bands of homosecasterol side-chain OH groups bound by an intermolecular H-bond. The homocastasterone diol groups also form intramolecular Hbonds more actively. The lack of the diol group in ring A of the homosecasterols does not affect the frequencies of the C=O stretching vibrations. This leads to the conclusion that the C=O group forms intermolecular H-bonds only with the side-chain OH groups of brassinosteroids pressed in KBr.     

Fluorescent properties and symmetry of the monodeprotonated form of 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin

The spectral and kinetic properties of the monodeprotonated form of the cationic 5,10,15,20-tetrakis(4-Nmethylpyridyl) porphyrin (H₂TMPyP) in solution are studied. The experimental results obtained are interpreted based on the four-orbital Gouterman model. It is established that the monodeprotonated form HTMPyP⁻ can be assigned to the D4h symmetry point group, and has spectral and photophysical characteristics similar to the characteristics of the fluorescent metal complexes of H₂TMPyP with relatively low electronegativity of the chelated metal ion. It is hypothesized that formation of the monodeprotonated form HTMPyP⁻ is accompanied by a decrease in the oxidation potential of the porphyrin molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 613–619, September–October, 2006.     

Calculation of the IR spectrum of (22S,23S)-24-epicastasterone

Normal vibrational frequencies and absolute IR band intensities for the biologically active steroidal phytohormone (22S,23S)-24-epicastasterone have been calculated within the framework of an original combined approach that uses classical normal coordinate analysis by means of the molecular mechanics method coupled with the quantum-chemical estimation of absolute intensities. Absorption bands in the IR spectrum of this molecule in the region 1500-900 cm⁻¹ were first interpreted based on a comparison of the experimental IR spectrum with the calculated optical-density spectral curve. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 768–775, November–December, 2008.     

Infrared and Raman spectra of Histidine: an ab initio DFT calculations of Histidine molecule and its different protonated forms

The infrared spectra of Histidine molecule have been recorded in the Nujoll mull as well as in aqueous solution in the range 400–4000 cm⁻¹. The Raman spectrum of the same molecule has also been measured. The different protonated/deprotonated forms of imidazole ring which contains different forms of Histidine1, Histidine2, Histidine3 and Histidine4 have been studied with DFT and RHF methods using several basis sets. A comparison of energies of the two neutral tautomers (Histidine1 and Histidine2) indicates that Histidine1 is more stable as compared to Histidine2 while Histidine3 (imidazolium cation) is the most stable in gas phase. The selected geometrical parameters and theoretically calculated frequencies for the above-mentioned form of Histidine were also proposed. The observed IR and Raman bands of Histidine molecule are assigned to different modes on the basis of calculated frequencies, their intensities and available literature values.     

Infrared spectra of BeSO4.4H2O and its deuterated analogue in 4000–1200 cm−1 region

IR spectra of BeSO₄.4H₂O and its deuterated analogue at ∼300 K and ∼110 K are reported in the region 4000–1200 cm⁻¹ using thin film and nujol mull techniques. The observed bands have been assigned as the internal modes of the water and the overtones and combinations of various modes using the recently revised assignments of SO₄ ²⁻ and Be(aq)₄ fundamentals in the region 1200–250 cm⁻¹ (Srivastavaet al 1976). The splitting of the internal modes of water has been discussed in the light of the effects of deuteration and cooling and it is shown that all the water molecules in a unit cell are asymmetric but crystallographically equivalent.     

Vibrational spectra and crystal lattice dynamics of hexahydrates of zinc potassium and ammonium sulfates

The IR spectra and polarized Raman spectra of crystals of hexahydrates of zinc potassium and ammonium sulfates have been obtained experimentally at 93 K and at room temperature. The frequencies and modes of normal vibrations of the octahedral complex [Zn(H₂O)₆]²⁺ have been calculated. The assignment of the observed lines of the internal and external vibrations of the crystal cell has been made by calculations and by factor-group analysis. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 162–168, March–April, 2000.     

Dissociation of molecular hydrogen ions by an IR laser pulse

Dissociation dynamics of the simplest molecular systems, such as H₂ ⁺, D₂ ⁺ and HD⁺ ions, in an intense IR laser field has been investigated by numerical modeling. An n-term approximation has been developed to describe the molecular system dynamics in an intense electromagnetic field. Calculations by the n-term approximation have been compared to an accurate numerical solution of the two-particle problem. The dissociation probability as a function of the frequency and intensity of radiation for different isotopes in a molecular hydrogen ion is discussed. A quasistatic model of molecule dissociation in an IR field has been suggested, and limits of its applicability have been determined. Zh. éksp. Teor. Fiz. 113, 128–143 (January 1998)     

Interpretation of vibrational spectra of a closed form of indoline spirophenanthroxazine

We have measured IR and Raman spectra of molecules of a closed form of the photochromic compound indolinespirophenanthroxazine. Using the density-functional method, we have optimized the structures of the closed and open forms of this molecule and calculated its normal vibrations. Based on these calculations, we propose an interpretation of the obtained vibrational spectra. We have determined the spectral range of manifestation, 700–900 cm^?1, and have found wavenumbers of normal vibrations through which the spiro structure of the indolinespirophenanthroxazine molecule in an excited state is likely to be rearranged into a merocyanine structure.     

Analysis of glucopyranoside trinitrate IR spectrum

The IR spectrum of 4-O-methyl-2,3,6-tri-O-nitromethyl-β-D-glucopyranoside has been interpreted in detail for the first time based on complete calculation of the normal vibration frequencies and absolute intensities of its IR absorption bands and a comparison of them with the corresponding experimental data. The results indicate that the location of the nitrates in cellulose nitrates can be determined experimentally from separate components of complicated absorption bands in the ranges 1700–1600 and 900–800 cm⁻¹ of the IR spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 43–51, January–February, 2008.     

Vibrational spectra of thin eulytine films

This is a study of IR reflection spectra of systems of a thin Bi₄X₃O₁₂(X=Si, Ge) film and a substrate of fused quartz v-SiO₂ in the range 400–1600 cm⁻¹ at T=295 K. Bands assigned to Bi₄X₃O₁₂ are interpreted. It is found that single-photon processes are exhibited in the range 400–800 cm⁻¹, while biphonon processes, in the range 800–1600 cm⁻¹. I. Franko State University of Lvov, 50 Dragomanov St., 290005, Lvov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 494–498, July–August, 1997.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Optical and IR study of Li2O–CuO–P2O5 glasses

Infrared (IR) and UV spectra of ternary Li₂O–CuO–P₂O₅ glasses in two series Li₂O(65−X)%–CuO(X%)–P₂O₅(35%), X = 20, 30, 40 and Li₂O(55−X)%–CuO(X%)–P₂O₅(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm⁻¹ for P₂O₅(35%) and P₂O₅(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm⁻¹ which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm⁻¹ which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.     

Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

Infrared (IR) spectroscopy of chemisorbed C₆₀ on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm^-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C₆₀/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules. Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C₆₀ molecules, which results in rather small values (∼2×10⁹ s^-1 for Ag and Au, and ∼1.6×10⁹ s^-1for Cu), consistent with a marked metallic character of the adsorbed molecules. Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C₆₀ deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron–phonon coupling with induced surface states. Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002