Quantum chemical calculation of normal molecular vibrations for substituted five-member chalcogen heterocyclic compounds taking anharmonicity into account

The DFT/B3LYP/6-31G* method is used in an anharmonic approximation to analyze the vibrational spectra of substituted furan, thiophene, and selenophene (3,4- and 2,5-dimethyl-, dichloro-, and diaza-; and 2,3,4,5-tetrachloro-). The influence of resonance effects is clarified. in final form, December 16, 2008. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 170–175, March–April 2009.     

Anharmonic Analysis of the Vibrational States of Phenyldichlorarsine and Phenyldichlorphosphine

Using the DFT/B3LYP method with the basis set 6-31G*(**), we analyzed the vibrational spectra of the conformers phenyldichlorarsine and phenyldichlorphosphine in the anharmonic approximation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 557–559, July–August, 2005.     

Anharmonic resonances in the vibrational spectra of pyrazine

The quartic force field of pyrazine has been calculated in the B3LYP/6-31G(d) hybrid density-functional approximation. Based on the results of this calculation, the total IR (250–3800 cm^–1) and Raman (400–3200 cm^–1) spectra of pyrazine have been interpreted with consideration for the Fermi and Darling-Dennison resonances and their spectral manifestations. A precision method is proposed for anharmonic analysis of the vibrational states of polyatomic molecules on the basis of consideration of their theoretical anharmonicity constants in combination with the corresponding experimental frequencies. The method of linear scaling of frequencies has been theoretically substantiated.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 13–22, January–February, 2005.     

Vibrational spectra and structural dynamic models of halosubstituted formaldehyde

The DFT/B3LYP method with 6-31G*(**) basis sets has been used to analyze the vibrational spectra of halo-substituted formaldehyde in the anharmonic approximation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 683–686, September–October, 2006.     

Structural dynamic models and anharmonic analysis of vibrational states of polychloro-substituted dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxin

We have analyzed the vibrational spectra of β-tetrachloro-substituted and ortho-chlorosubstituted dibenzo-p-dioxin using the DFT/B3LYP/6-31G(d) method, in the anharmonic approximation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 21–24, January–February, 2007.     

Vibrational spectroscopy of tolane; Coriolis coupling between Raman-active modes of g symmetry

ABSTRACT

Vibrational spectroscopy of tolane (diphenylacetylene), which has 66 normal modes, has been advanced. Anharmonic wavenumber predictions were made with the quartic potential energy surface obtained with B3LYP/cc-pVTZ model and the second-order perturbation theory (VPT2). Infrared (IR) intensity and Raman activities were computed at the harmonic level. The IR spectrum of the crystal and Raman spectra of the liquid and the crystal tolane were newly recorded. The lingering problem of an excess of polarised Raman bands at wavenumbers appropriate for fundamentals, other than a_g modes, has now been attributed to Coriolis coupling within modes of g symmetry species. Consequently, D_2h point symmetry group has been confirmed for a planar tolane molecule. Assignments for almost all fundamentals of tolane are now secure. The assignment for ν₃₂ remains questionable. Remaining unassigned fundamentals are: ν₃₄ and ν₃₅, which, as a_u symmetry species, are IR- and Raman-inactive transitions, and ν₅₉(b_2u), which is predicted to have a very low wavenumber.     

用代数哈米顿量研究CH3C1分子的振动谱

我们提出一种描述XH3分子的伸缩和弯曲振动的U(2)代数哈米顿量,其中包括了伸缩和弯曲振动的费米共振耦合;用它来拟合CH3Cl分子的实验数据,结果表明有较少参数的代数模型算得的偏差比其它模型算得的偏差要小.     

用代数哈米顿量研究CH_3Cl分子的振动谱(英文)

我们提出一种描述XH3分子的伸缩和弯曲振动的U(2)代数哈米顿量,其中包括了伸缩和弯曲振动的费米共振耦合,用它来拟合CH3Cl分子的实验数据,结果表明有较少参数的代数模型算得的偏差比其它模型算得的偏差要小.     

SO2: High-resolution analysis of the (0 3 0), (1 0 1), (1 1 1), (0 0 2) and (2 0 1) vibrational states; determination of equilibrium rotational constants for sulfur dioxide and anharmonic vibrational constants

High resolution Fourier transform spectra of a sample of sulfur dioxide, enriched in ³⁴S (95.3%). were completely analyzed leading to a large set of assigned lines. The experimental levels derived from this set of transitions were fit to within their experimental uncertainties using Watson-type Hamiltonians. Precise band centers, rotational and centrifugal distortion constants were determined. The following band centers in cm⁻¹ were obtained: ν₀(3ν₂)=1538.720198(11), ν₀(ν₁ + ν₃)=2475.828004(29), ν₀(ν₁ + ν₂ + ν₃)=2982.118600(20), ν₀(2ν₃)=2679.800919(35), and ν₀(2ν₁ + ν₃)=3598.773915(38). The rotational constants obtained in this work have been fit together with the rotational constants of lower-lying vibrational states [W.J. Lafferty, J.-M. Flaud, R.L. Sams, EL Hadjiabib, J. Mol. Spectrosc. 252 (2008) 72-76] to obtain equilibrium constants as well as vibration-rotation constants. These equilibrium constants have been fit together with those of ³²S¹⁶O₂ [J.-M. Flaud, W.J. Lafferty, J. Mol. Spectrosc. 16 (1993) 396-402] leading to an improved equilibrium structure. Finally the observed band centers have been fit to obtain anharmonic rotational constants.     

Structural Dynamic Models and Vibrational Spectra of Nitrobenzene and Nitropyridines

Using the DFT/B3LYP method with the basis sets 6-31G*(**), we analyzed the vibrational spectra of nitrobenzene and nitropyridines for free molecules and their solutions in water, ethanol, and benzene. The influence of a solvent on the behavior of the characteristic spectral parameters of nitrobenzene is revealed, and the assignment of vibrations for nitropyridines is given. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 450–453, July–August, 2005.     

A reevaluation of the assignment of the vibrational fundamentals and the rotational analysis of bands in the high-resolution infrared spectra of trans- and cis-1,3,5-hexatriene

Assignments of the vibrational fundamentals of cis- and trans-1,3,5-hexatriene are reevaluated with new infrared and Raman spectra and with quantum chemical predictions of intensities and anharmonic frequencies. The rotational structure is analyzed in the high-resolution (0.0013-0.0018 cm⁻¹) infrared spectra of three C-type bands of the trans isomer and two C-type bands of the cis isomer. The bands for the trans isomer are at 1010.96 cm⁻¹ (ν₁₄), 900.908 cm⁻¹ (ν₁₆), and 683.46 cm⁻¹ (ν₁₇). Ground state (GS) rotational constants have been fitted to the combined ground state combination differences (GSCDs) for the three bands of the trans isomer. The bands for the cis isomer are at 907.70 cm⁻¹ (ν₃₃) and 587.89 cm⁻¹ (ν₃₅). GS rotational constants have been fitted to the combined GSCDs for the two bands of the cis isomer and compared with those obtained from microwave spectroscopy. Small inertial defects in the GSs confirm that both molecules are planar. Upper state rotational constants were fitted for all five bands.     

Molecular structure,NMR and vibrational spectral analysis of 2,4‐difluorophenol by ab initio HF and density functional theory

Quantum chemical calculations of energies, geometries and vibrational wavenumbers of 2,4‐difluorophenol (2,4‐DFP) were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6‐311G(d,p) as basis set. The optimized geometrical parameters obtained by HF and DFT calculations are in good agreement with related molecules. The best level of theory in order to reproduce the experimental wavenumbers is the B3LYP method with the 6‐311G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of 2,4‐DFP is also reported. The entropy of the title compound was also performed at HF/6‐311G(d,p) and B3LYP/6‐311G(d,p) levels of theory. The isotropic chemical shift computed by ¹H, ¹³C NMR analyses also shows good agreement with experimental observations. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule have been constructed. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical analysis of vibrational spectra of tautomeric purine forms

A theoretical analysis of vibrational spectra of purine tautomers was carried out using the DFT/B3LYP/6-31G(d)* method. The influence of intermolecular interaction in purine dimers was estimated. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 23–27, January–February, 2008.     

Experimental vibrational spectra (Raman,infrared) and DFT calculations on monomeric and dimeric structures of 2‐ and 6‐bromonicotinic acid

In this work, the Fourier transform infrared and Raman spectra of 2‐bromonicotinic acid and 6‐bromonicotinic acid (abbreviated as 2‐BrNA and 6‐BrNA, C₆H₄BrNO₂) have been recorded in the region 4000–400 and 3500–50 cm⁻¹. The optimum molecular geometry, normal mode wavenumbers, infrared intensities and Raman scattering activities, corresponding vibrational assignments and intermolecular hydrogen bonds were investigated with the help of B3LYP density functional theory (DFT) method using 6‐311++G(d,p) basis set. Reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated with scaled quantum mechanical (SQM) method. From the calculations, the molecules are predicted to exist predominantly as the C1 conformer. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular structure,vibrational spectroscopic studies and NBO analysis of the 3,5‐dichlorophenylboronic acid molecule by the density functional method

In this study, the Fourier‐transform infrared (FT‐IR) and FT‐Raman spectra of 3,5‐dichlorophenylboronicacid (3,5‐dcpba) were recorded in the solid phase. The structural and spectroscopic analysis of the 3,5‐dichlorophenylboronic was made by using density functional harmonic calculations. There are three conformers for this molecule. The computational results diagnose the most stable conformer of 3,5‐dcpba as the ct form. The geometrical parameters and energies have been obtained for all three conformers from DFT (B3LYP) with 6‐311+ + G(d,p) basis set calculations. The vibrations of stable and unstable conformers of 3,5‐dcpba are researched by using quantum chemical calculations. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with the scaled quantum mechanics (SQM) method. The stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using the natural bond orbital (NBO) analysis. The results show that the charge in electron density (ED) in the π* and σ* antibonding orbitals and E2 energies confirms the occurrence of ıntermolecular charge transfer (ICT) within the molecule. Finally, the calculation results were applied to simulated infrared and Raman spectra of the title compound, which show agreement with the observed spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Theoretical interpretation of the vibrational spectra of methyl-substitutedS-triazine

The problems of normal vibrations of mono-, di-, and trimethyl-substituted S-triazine are solved. Assignments of the frequencies of fundamental vibrations for an aromatic ring and methyl groups are suggested. Corrections for methyl substitution for the force constants of S-triazine are determined. The groups of characteristic and noncharacteristic vibrations of the aromatic ring of S-triazine on substitution of hydrogen are established. Saratov State University, 83, Astrakhanskaya St., Saratov, 410601, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 322–325, May–June, 1998.     

Comparison of theoretical and experimental studies of infrared and microwave spectral data for 5- and 6-membered ring heterocycles: The rotation constants, centrifugal distortion and vibration rotation constants

A systematic study of the rotation constants, vibration-rotation constants and quartic centrifugal distortion constants has been performed for furan, pyrrole, thiophene, both oxazoles and thiazoles, 1,2,4- and 1,2,5-oxa- and -thiadiazoles, 1,2,5-selenadiazole, and several 6-membered heterocycles (azines). The main study used cc-pVTZ basis sets. There is a very close correlation between the observed constants above and those calculated, especially using the cc-pVTZ + B3LYP procedures; some trends in these appear on substitution of HC by N in the azoles. This strong correlation between experimental values and this theoretical procedure is also apparent with vibrational differences in rotation constants, all over large numbers of measured values. However, a small number of calculated values do not correlate well with experiment; this may be a result of some of the experimental values being subject to resonance perturbations not included in the calculations. In general, a TZ2P basis set with B3LYP methodology, and cc-pVTZ results with MP2 methodology, lead to correlations of similar quality, but the latter require markedly more computing power. The present study draws attention to a tetrad in the IR spectrum of 1,2,5-oxadiazole, where further analysis is necessary.     

Effects of Neutral and Anionic Substituents on the Carbonyl Stretching Band of Substituted Benzophenones

Satisfactory correlations were found of the frequencies of the title band (ν_CO) with 6⁺ and other substituent constants. The correlations proved valid for benzophenones with both neutral and anionic substituents (more than 100 compounds). The integrated intensities of the ν_CO bands (A^1/2 _CO) did not correlate with any type of substituent constants; the decrease in A_CO in the cases of benzophenones with strong electron-releasing substituents was ascribed to a resonance-induced intensity borrowing from ν_CO BY THE aromatic skeletal bands (8-type). This statement wa confirmed by IR data few deuterated benzophenones.     

A DFT/TD‐DFT study for the ground and excited states of peramine and some pyrrolopyrazinone compounds

Peramine, a heterocyclic natural molecule, reveals two main, different in nature, electronic absorption bands. Theoretical calculations at the TD‐B3LYP/6–311++G(d,p) level of theory show that the electronic excitations are connected predominantly with π → π^* and charge‐transfer (CT) transitions. Excitation of electrons from the pyrrolopyrazinone ring to the side chain plays a role in creating the CT transition. The character and energy of the first 30 singlet–singlet electronic transitions have also been investigated for the most stable conformation of peramine. Copyright © 2009 John Wiley & Sons, Ltd.     

Temperature dependence of the linewidth of the first-order Raman spectra for MnF2 crystal

The first-order Raman spectra ofE _gandA _1g modes in MnF₂ crystal were measured at temperatures from 4.2 to 563 K, and the values of the linewidths obtained. The temperature dependence of the linewidths was analyzed by the phonon dispersion curves based on the rigid ion model, and the result showed that it was caused approximately by the cubic anharmonic term in crystal potential energy.