The vibrational spectrum of anisole

The infrared and Raman spectra of C₆H₅OCD₃, C₆D₅OCH₃ and C₆D₅OCD₃ have been recorded in the liquid state. Vibrational assignments have been made and values for most of the fundamental vibrations have been obtained and correlated with those of C₆H₅OCH₃. Studies of the ultraviolet absorption spectrum have provided gas-phase data on a number of totally symmetric modes.     

Homoclinic motions in the vibrational spectra of floppy systems: the LiCN molecule

Recent experimental and theoretical methods allowed the efficient investigation of highly excited rovibrational states of molecular systems. At these levels of excitation the correspondence principle holds, and then classical mechanics can provide intuitive views of the involved processes. In this respect, we have recently shown that for completely hyperbolic systems, homoclinic motions, which are known to organize the classical chaotic region in Hamiltonian systems, imprint a clear signature in the corresponding highly excited quantum spectra. In this Communication we show that this result also holds in mixed systems, by considering an application to the floppy LiNCLiCN molecular system.     

Scaling factors for the prediction of vibrational spectra. I. Benzene molecule

The performance of semiempirical, ab initio, and density functional methods in calculating and describing the vibrational frequencies of benzene was determined. Different levels were used. The modes were characterized by the magnitude and direction of the displacement vector. The error in the calculated frequencies was reduced using two procedures to obtain the scaled frequencies. Scaling equations were determined for each theoretical method. Specific scale factors were calculated to reduce the error in the ring modes of benzene derivatives. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 661–684, 2000     

Theoretical calculations of the vibrational spectra of the complex LibeF3 molecule

Ab initio calculations of the structure, force field, frequencies and intensities of normal modes of the LiBeF₃ molecule have been carried out, using basis sets of Huzinaga and Dunning in a double-zeta contraction. The calculated results are compared with the infrared spectrum of LiBeF₃ in an inert matrix obtained by Snelson et al.     

Analysis of the vibrational spectra of chiral liquid crystalline thioesters

Vibrational spectra of (S)-(+)-4-(1-methylheptyloxy)biphenyl 4-pentylphenylthiobenzoate (MHOBS5) were calculated using the density functional theory method, with two different basis sets, the 6-31G* and the 6-31+G*. The force fields were scaled using the scaled quantum-mechanical force field (SQM) procedure. Various sets of scaling factors for the SQM procedure are discussed. Results of simulations were used to analyse the experimental data obtained from infrared and Raman experiments for MHOBS5 and the homologous MHOBS4.     

Prediction of vibrational spectra from microwave spectra

Explicit and simple relations are derived for the Kivelson-Wilson parameters which can directly generate the vibrational spectrum of XY₂ bent type molecules. These relations are also shown to generate the above parameters for the different isotopes of a parent molecule. These predictions are verified in the case of some molecules of the above symmetry for which experimental microwave studies have been made.     

Scaling factors for the prediction of vibrational spectra. II. The aniline molecule and several derivatives

The structure of aniline was studied by semiempirical, ab initio, and density functional methods. Complete geometry optimization of the minimum energy structure and of the transition states for internal rotation and inversion of the amino group was carried out using several levels. The performance of the different methods in calculating and describing the vibrational frequencies of aniline was determined. The normal modes were characterized by the magnitudes and direction of the displacement vectors. Three procedures were used to obtain the scaled frequencies, two of them new, using specific scale factors and scaling equations from the benzene molecule. The errors obtained were compared with those calculated through other standard procedures. A reassignment of several bands was made. A comparison of the cost‐effective method and procedure of scaling was carried out. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Numerical-analytic implementation of the higher-order canonical Van Vleck perturbation theory for the interpretation of medium-sized molecule vibrational spectra

Anharmonic vibrational states of semirigid polyatomic molecules are often studied using the second-order vibrational perturbation theory (VPT2). For efficient higher-order analysis, an approach based on the canonical Van Vleck perturbation theory (CVPT), the Watson Hamiltonian and operators of creation and annihilation of vibrational quanta is employed. This method allows analysis of the convergence of perturbation theory and solves a number of theoretical problems of VPT2, e.g., yields anharmonic constants y(ijk), z(ijkl), and allows the reliable evaluation of vibrational IR and Raman anharmonic intensities in the presence of resonances. Darling-Dennison and higher-order resonance coupling coefficients can be reliably evaluated as well. The method is illustrated on classic molecules: water and formaldehyde. A number of theoretical conclusions results, including the necessity of using sextic force field in the fourth order (CVPT4) and the nearly vanishing CVPT4 contributions for bending and wagging modes. The coefficients of perturbative Dunham-type Hamiltonians in high-orders of CVPT are found to conform to the rules of equality at different orders as earlier proven analytically for diatomic molecules. The method can serve as a good substitution of the more traditional VPT2.     

Quantum chemical predictions of the vibrational spectra of polyatomic molecules. The uracil molecule and two derivatives

This work describes the different scaling procedures used to correct the quantum-chemical theoretical predictions of the IR and Raman vibrational wavenumbers. Examples of each case are shown, with special attention to the uracil molecule and some derivatives. The results obtained with different semiempirical and ab initio methods, and basis sets, are compared and discussed. A comprehensive compendium of the main scale factors and scaling equations available to obtain the scaled wavenumbers is also shown.     

High resolution electronic absorption spectra of anisole and phenoxyl radical

High resolution absorption spectra of anisole and phenoxyl radical has been recorded in the vapor phase at room temperature by flash photolysis technique, and subsequent reactions have been investigated by kinetic spectroscopy. It was possible to follow the kinetics of the radical's decay which occurred predominantly by bimolecular recombination. The concentration of the phenoxyl radical calculated from the concentration of diphenoxyl molecules formed in the reaction cell during the optical pumping. The absolute extinction coefficient of this radical was measured from the absorption band at 291 nm, and found to be 0.95 x 10(+4) mol(-1) 1 cm(-1).     

Terahertz vibrational spectra of metallocene

The terahertz transmission spectra of crystalline metallocenes and decamethyl metallocene were clearly measured in the range of 0.7-6.2 THz by a recently developed GaP Raman terahertz spectrometer. The low-frequency mode of ring-metal-ring bending and CH₃ out-of-plane oscillation were observed, and the force constants of bending were estimated from the absorption frequencies based on a three-body model.     

The vibrational spectra of phthalimide

The polarised i.r. and Raman spectra from three orthogonal faces of single crystalline phthalimide have been measured. Supplemented by information from solution spectra (depolarisation ratios from the Raman spectra), it is possible to assign the fundamental vibrations for the molecule almost completely. The experimental assignments are confirmed by an approximate normal coordinate calculation.     

On the vibrational spectra of liquid HCl

We report quantitative measurements of the infrared spectra intensities and of the Raman cross section for liquid HCl. The local field effect and the induced dipole moment account for the observed intensity enhancement. Our calculation is based on the reaction field approach. On the other hand, we show that the local field effect and the dipolar term in the intermolecular interaction energy are not sufficient to explain the frequency shift. We also show that the first overtone is mainly due to simultaneous transitions of two molecules from the ν = 0 to the ν = 1 levels and our calculations give the right order of magnitude of its intensity. Finally, we can reproduce the lineshape of the first overtone by a dissipative coupling which is derived from Redfield's theory of relaxation.