Metallomethanes: XIII. Vibrational spectra and force fields of cyanomercuriomethanes

Vibrational spectra with assignments and results of normal coordinate calculations for cyanomercuriomethanes CH_4−n(HgCN)_n (2 ≤ n ≤ 4) are discussed. The valence force constants of the central CHg bonds are 2.149, 1.944, and 1.798 N cm⁻¹,while those of the HgCN bonds are 2.204, 2.123, and 2.162 N cm⁻¹, for n = 2, 3 and 4, respectively. All these force constants are lower than the corresponding constants for methylmercury cyanide (2.445 and 2.379 N cm⁻¹). The overall behaviour of these force constants as a function of the degree of mercuration n is quite similar in both the cyanomercuriomethanes CH_4−n(HgCN) and methylmercuriomethanes CH_4−n(HgCH₃)_n series with the difference that there are variations in the constants at higher values in the former series. The potential energy distributions indicate that the valence vibrations of the CH, CN, and HgCN bonds are almost independent of all other vibrations, which in turn are more or less strongly coupled.     

Vibrational spectra,force fields and electronic structures of sydnones

Normal vibrational analyses of 3-methylsydnone and 3-methylsydnone-d₄ have been performed. On the basis of the set of force constants obtained, the electronic distribution within the mesoionic ring is evaluated and compared to the results of MO calculations. The π-bond order of the sydnone carbonyl group is shown to be lower than that in alicyclic esters and the unusually high “carbonyl stretching” frequency is due to the contributions from other coordinates to this mode. The splitting of the “carbonyl stretching” band observed in the spectra of 3-methylsydnone and of related derivatives is explained by the strong kinematic coupling between mesoionic bonds.     

Vibrational spectra and harmonic force fields of pyrrolidine derivatives: comparison between HF, MP2 and DFT force fields

Infrared and Raman spectra are reported for the isotopic species of pyrrolidine-d₀ (PY) and -d₁ and for N-methylpyrrolidine-d₀ (NMP), -d₂, -d₃ and -d₈. A complete assignment of the experimentally observed bands to normal modes is presented and discussed in particular in the CH/CD stretching region. The molecular structures and harmonic force fields were calculated ab initio at the Hartree–Fock (HF), the second order Møller–Plesset (MP2) and the density functional theory (DFT) level with the 6-31G* basis set. The force fields were fitted by use of 7 (PY) and 4 (NMP) independent scale factors. The spectra calculated with the DFT force fields are in better agreement with the experiment than those calculated by the MP2 and HF force fields. Though some scaled fundamental frequencies show larger deviations from the experimental ones, the mean percentage deviations of calculated frequencies from experimental fundamentals are less than 2.6% for all isotopic species of PY and NMP under study. The results indicate that density functional theory is a reliable tool to get a deeper insight in the assignment of vibrational spectra and the nature of normal modes of pyrrolidine derivatives.     

Vibrational spectra and force field of dimethylphosphines

Vibrational spectra in the range 200–3000 cm^?1 are reported and assigned for the species (CH₃)₂PH, (CH₃)₂PD, (CD₃)₂PH, (CD₃)₂PD, CH₃CD₃PH and CH₃CD₃PD. The spectra in the range 1020–500 cm^?1 are complicated due to the coupling between δPH, ?Me and the skeletal modes of the molecule. Interpretation is only possible through a force field which is markedly different from an earlier one of dimethyl sulphide. This force field predicts uncoupled δPH frequencies of 835 (a) and 909 cm^?1 (a), couples PH bending largely to out-of-skeletal plane methyl rocking (?_i) and includes a low p¦¦(a) bending constant, a high skeletal bending constant and unusual signs for two interaction constants. In the crystalline phase at 78 K, the two methyl groups are non-equivalent.     

Vibrational spectra and force field of terephtalonitrile

The IR and Raman spectra of the two molecules terephtalonitrile and terephtalonitrile-¹⁵N were recorded to permit the general assignment of the vibrational bands observed, in agreement with a D_2h symmetry for these molecules. The general quadratic force field was calculated by the semi-empirical MINDO/3 method from an optimized geometry obtained by the same method. The resulting force field was refined by employing the experimental vibrational frequency data of the two molecules and those of terephtalonitrile-d₄. The final differences between the calculated end experimentally observed frequencies for B_2g and B_3u terephtalonitrile species were within the range ± 0.1 cm⁻¹.     

Vibrational spectra and force field of azacyclic compounds. I. Pyrrole

For the molecules of pyrrole and its symmetric deuterated derivatives, vibrational spectra have been analyzed, and the force field has been defined in natural coordinates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 29, No. 5, pp. 651–655, May, 1993.     

Vibrational spectra and force constants ofS-methyl-N,N-dimethyldithiocarbamate

The IR and Raman spectra ofS-methyl-N,N-dimethyldithiocarbamate were studied in different phase states. The frequencies and vibration modes of normal vibrations were analyzed, and the erroneous assignments made in some previous works were corrected. The force constants of the molecule were estimated using the model of the generalized valenceforce field.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1108–1110, June, 1995.This work was carried out with partial financial support from the International Science Foundation.     

Vibrational spectra and valence force field calculation of deltic acid

Infrared and Raman spectra of crystalline deltic acid and its deuterated derivative have been studied between 4000 and 20 cm⁻¹. In order to specify vibrational assignment of ring and CO modes based on C_2v molecular symmetry, valence force field calculation was undertaken. It appears that the results obtained for simpler disubstituted cyclopropenones can be applied to deltic acid. So, the highest frequencies about 1930 and 1610 cm⁻¹ involve nearly equal mixture of ring and CO stretching. Two different, strong but asymmetric OH

OC hydrogen bonds occur in crystal.     

Vibrational spectra of benzonitrile-p-d and benzonitrile-d5 and force field of benzonitrile

The i.r. and the Raman spectra of benzonitrile-p-d have been recorded and twenty-three of the fundamental vibrations of benzonitrile-p-d and five of those of benzonitrile-d₅ have been reassigned. A normal coordinate analysis for benzonitrile and its p-d and d₅ derivatives has been carried out. By using a set of valence type force constants, a good fit between the observed and the calculated frequencies has been obtained.     

Vibrational anharmonicity and harmonic force fields for dichloromethane from quantum-chemical calculations

Anharmonic and related constants have been calculated for CH2Cl2, CD2Cl2, and CHDCl2 by using the program Gaussian03 and B3LYP and MP2 models. Bases used were 6-311++G** and cc-pVTZ. The size of grid used in the B3LYP/6-311++G** model had a noticeable effect on resulting data. Features of the MP2/6-311++G** calculations suggested a deleterious effect of the absence of f functions in this basis set. The need for the replacement of second-order terms in the perturbation theory formulas for the vibrational anharmonic constants x ij in the presence of Fermi resonance was explored, and minor resonances were found associated with the cubic constants varphi 122 and varphi 299 (d 0 isotopomer), phi122 and phi849 (d2), and phi278 (d1). Computed xij values for nuCH and nuCD motions agree quite well with earlier experimental data. Observed anharmonic frequencies, nu obsd, were corrected to "observed" harmonic frequencies, omega obsd, by using computed differences Delta = omegaQC-nuQC. These differences Delta are larger for the antisymmetric nuasCH2 mode than for symmetric nusCH2 motion. This fact made it necessary to use differing scale factors for the two kinds of CH stretching force constants in a subsequent scaling of the harmonic force field to nuobsd. Force field scaling was also carried out by refining to omega obsd. In both approaches, the B3LYP models required differing scale factors for symmetric and antisymmetric CCl stretching force constants, indicating a failure to compute an accurate C-Cl stretch-stretch interaction force constant. The MP2/cc-pVTZ force field was preferred. Both scaled and unscaled harmonic force fields were used to calculate centrifugal distortion constants (CDCs) and contributions to the vibrational dependence of the rotational constants (alphas). Variations in the CDCs can, in part, be explained by the magnitudes of the frequencies used in the scaling process.     

Theoretical studies of force fields and IR spectra of isocytosine

The optimized geometries, complete harmonic force fields, and infrared intensities of isocytosine tautomers, amino‐hydroxy and amino‐oxoN(1)H, were calculated at the ab initio Hartree–Fock level using the 6‐31G* basis set. The theoretical force fields were scaled by empirical scale factors, which were determined by fitting to the IR spectrum of the amino‐oxo form and were then transferred to the amino‐hydroxy form. The average deviations between experimental and computed frequencies are 7.6 cm⁻¹ for amino‐oxo and 9.5 cm⁻¹ for amino‐hydroxy, respectively. The assignments of the fundamental frequencies and the transferability of the force constant scale factors are also presented. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 53–60, 1999     

Vibrational spectra and molecular force field of N-methylpyridinium ion and some deuterated derivatives

The vibrational spectra of N-methylpyridinium iodide and three of its selectively deuterated derivatives have been recorded in the crystalline as w     

Structure, force fields, and vibrational spectra of cerium tetrahalides

The geometrical structure, force fields, and vibrational spectra of CeX₄ (X = F, Cl, Br, I) were investigated by second, third, and fourth order Möller-Plesset perturbation theory, CISD+Q configuration interaction method, and the CCSD(T) coupled cluster method. Calculations on CeF₄ were also performed by multiconfiguration second order perturbation theory MCQDPT2/CASSCF. The wave function of the ground state of CeX₄ molecules was found to be appreciably non-one-configurational; this property increases from cerium fluorides to iodides and leads to the divergence of the series of Möller-Plesset perturbation theory. The calculated data point to a tetrahedral equilibrium nuclear configuration in CeX₄ molecules. The energy barriers to the inversion of the tetrahedral CeX₄ molecules via the square configurations are high enough, 74–89 kJ/mol. The calculated vibration frequencies, effective internuclear distances, and mean amplitudes of nuclear vibrations in CeF₄ agree with IR and Raman spectroscopic and high-temperature gas-phase electron diffraction data.     

Laser Raman and IR spectra and force fields for 2,4-dichlorobenzonitrile

Raman spectrum of 2,4-dichlorobenzonitrile (2,4-DCBN) in powder form has been recorded in the region 50-4000 cm(-1) on a Jasco K-500 Raman spectrophotometer using the 488.0 nm radiation from an argon laser. FTIR spectra in the region 200-4000 cm(-1) have been recorded in KBr pellet and nujol mull on a Nicolet DX spectrometer. Using the observed Raman and IR frequencies, normal co-ordinate analysis has been carried out to support the vibrational analysis and to determine the planar and non-planar force fields.