A vibrational CASSCF study of stretch-bend interactions and their influence on infrared intensities in the water molecule

Summary An extension of the multiconfigurational SCF approach for the resolution of the vibrational problem is presented; it follows the philosophy of the CASSCF method developed in Quantum Chemistry. The new method allows a more complete treatment of anharmonic mode couplings, converges much faster and gives a clearer physical insight of vibrational interactions. This is exemplified by the calculation of infrared transition moments in the H₂O and D₂O isotopomers of the water molecule. It is shown how this property varies with the quality of the wave function when vibrational resonances occur. A detailed analysis by means of this new VCASSCF method demonstrates the crucial importance of excited bending oscillators in the intensity of some pure stretching transitions.Boursier F.R.I.A.     

Normal coordinate analysis of MSiH3 moieties in transition metal complexes and comparison to results obtained for silyl halides

In order to examine the influence of the transition metal on the metal-silyl fragment MSiH₃ and the metal-silicon bond, polarized Raman spectra of the complexes (C₅R₅)(CO)₂FeSiH₃ R = H (Cp) (1a), Me (Cp^*) (1b)], (C₅H₅)(CO)(PPh₃)FeSiH₃ (1c), (C₅Me₅)(CO)₂RuSiH₃ (2), (C₅R₅)(CO)₂(PMc₃)MoSiH₃ [R = H (3a), Me (3b)], and (C₅R₅)(CO)₂(PMe₃)WSiH₃ [R = H(4a), Me (4b)] have been recorded. The spectral data have been evaluated and interpreted on the basis of a normal coordinate analysis of the MSiH₃ core and the derived force constants and potential energy distributions were compared to results obtained for analogous halogen derivatives in the series XSiH₃ [X = Br (5), I (6)].     

The role of rigid unit modes in negative thermal expansion

The rigid unit mode (RUM) model provides a valuable computational method to investigate correlations of transverse thermal motions of atoms important in negative thermal expansion (NTE) materials. We report here detailed RUM calculations of ten framework oxide structures that have been studied for their negative (or ultra low) thermal expansion properties. The results negate any simple and direct correlation between presence or absence of RUMs in a structure and its NTE property. All the structures considered can be viewed as networks of polyhedral connected by corners only. All evidence supports the importance the transverse motion of the atoms at the corners, but NTE does not correlate well with the presence RUMs for the polyhedra.     

Investigations with the finite element method on the Cyber 205

We are trying to investigate systematically the application of the finite element method (FEM) for solving the Schrödinger equation. The present paper is devoted to the calculation of vibrational transition probabilities for the collinear reactive system A + BC (i.e. H+H₂ and their isotopes). The calculations are fully two-dimensional and the results are compared with earlier FEM calculations and conventional basis set expansion methods using the the R-matrix or S-matrix propagation.We made extensive analysis of FEM on the vector-computer Cyber 205 and developed a vector code for the efficient use in two dimensions, so that in the near future applications even in three dimensions will be possible.For the hydrogen exchange reactions we investigated the following isotope combinations: (a) H + H₂, b) H + DH, D + HD and H + MuH (symmetric reaction), (c) D + HH, H + DD and Mu + DD (asymmetric reaction). We calculated the transition probabilities for up to five open vibrational channels and found excellent agreement with known exact values.     

On assignment of fundamental vibrational modes of hypophosphite anion and its deuterated analogue

Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results.     

Ab initio and DFT calculations for the structure and vibrational spectra of cyclopentene and its isotopomers

Ab initio calculations using the MP2/cc-pVTZ basis set do an excellent job of predicting the inversion barrier (247 vs. 232 cm⁻¹) and dihedral angle (26°) of cyclopentene. DFT calculations also do an excellent job of predicting the vibrational frequencies of the d₀, d₁, d₄, and d₈ isotopomers. They have also allowed the reassignments of several of the vibrational frequencies.     

Theoretical study on the molecule C30H20: five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage

Using geometry optimization and DFT method at the B3LYP/6-31G* level of theory for C₃₀H₂₀, an equilibrium geometry is identified that has the form of polyhedral hydrocarbon with five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage. Thus, this molecule is a tri-cage molecule with two pentaprismane cages and one dodecahedrane cage. Vibrational frequencies and the infrared spectrum are computed at the same level of theory. The heat of formation for C₃₀H₂₀ has been estimated in this paper. The heat of formation of C₃₀H₂₀ as well as the vibrational analysis indicates that this molecule enjoys sufficient stability to allow for its experimental preparation.     

The structural phase transitions of aminoguanidinium(1+) dihydrogen phosphate—study of crystal structures, vibrational spectra and thermal behavior

Aminoguanidinium(1+) dihydrogen phosphate was prepared by crystallization from aqueous solution. On the basis of the results of DSC measurements, X-ray structural analysis was carried out at temperatures of 160, 215 and 293 K for three aminoguanidinium(1+) dihydrogen phosphate phases ( |Z=2|non-ferroic |melting point 408 K; II |201-222 K|(2) |Z=2|non-ferroic|-; III |<201 K|(2)|Z=4|non-ferroic|-). The triclinic unit cell dimensions (a=6.8220(2), b=7.1000(2), c=7.4500(2) Å, α=86.925(2)°, β=80.731(2)°, γ=79.630(2)°, V=350.21(2) Å³—phase I) are similar for all three structural phases with the exception of phase III, where doubling of the c-axis length leads to an increase in the volume to 692.34(3) Å³. The crystal structure of all three modifications consists of parallel layers of dihydrogen phosphate anions that are interconnected by aminoguanidinium(1+) cations through hydrogen bonds of the N-H…O type. The planar aminoguanidinium(1+) cations are oriented almost parallel to each other and are perpendicular to the anion layers. The primary differences amongst phases I, II and III lie in the location of the H atom in the short O-H…O bonds connecting the dihydrogen phosphate anions in layers. The FTIR and FT Raman spectra of natural and deuterated compounds were recorded and interpreted. The FTIR spectra were studied down to a temperature of 90 K.     

A DFT analysis of the vibrational spectra of nitrobenzene

Raman and FTIR, spectra of nitrobenzene, nb, and its isotopomers, nb-¹⁵N, nb-¹³C₆ and nb-d₅, were obtained and the fundamental vibrational modes assigned with the aid of a B3LYP/6-311+G** calculation, without the need for scaling of the force constants. The changes in vibrational coupling between the nitro and benzene groups upon certain isotopic substitutions are well modelled by the calculation, which is able to reproduce the isotopic shifts in frequencies for the nitro vibrations, as well as changes in IR intensities.     

New chiral porphyrin-brucine gelator characterized by methods of circular dichroism

Herein, we report the first use of chiral alkaloid brucine to synthesize novel porphyrin-brucine conjugate capable of acting as a gelator of methanol and acetonitrile at extremely low level of concentration. The synthesis, characterization and spectral properties of gelator based on a novel structural motif, quaternized alkaloid conjugates, are described. Different spectroscopic methods (¹H NMR spectroscopy, Raman and infrared spectroscopy, and spectroscopy of electronic and vibrational circular dichroism) were used for characterization of the prepared organogel. The aggregation of the gelator studied by UV-vis spectroscopy and electronic circular dichroism showed the formation of chiral J-aggregates in water and water-methanol (1:1) mixture. A new methodology for the determination of functional groups involved in gel formation based on vibrational circular dichroism is presented.