Tunneling energy levels of an off-center impurity of the hydroxyl ion in NaCl crystal

Fine structures of the vibrational spectrum of OH^– in NaCl have been investigated by their dependence on the OH^– concentration, temperature and uniaxial stress. The absorption bands of A and C at 3651. 2 and 3655.2 cm-1 are ascribed to the tunneling motion of the off-center impurity of OH^–. The stress splitting factor of the tunneling levels has been estimated to be B(S11–S12)=0.96±0.10 cm-1/10⁸ dyn cm-2 in the ground state and it is about 1.4 times larger in the vibrational excited state.     

The LIF Excitation Spectrum of Jet-Cooled 2,6-Dicyano-3, 5-Dimethylaniline

The laser-induced fluorescence (LIF) excitation spectrum of jet-cooled 2, 6-dicyano-3,5-dimethylaniline (DCDMA) has been measured in the spectral range of 29,750–32,250cm^–1. The band origin at 29,860.8 cm^–1 and as many as 250 vibrational bands have been identified in the excitation spectrum. The analysis of the excitation spectrum of DCDMA gives more than 28 vibrational modes involving aromatic ring oscillations and oscillations related to the substituent groups. DCDMA is nonplanar in the ground state, with the NH₂ plane at about 9° with respect to the molecular plane (RHF/6-31G*). The singlet excited molecule is planar (CIS/6-31G*). Both CIS/6-31G* and CASPT2 calculations predict that the lowest excited state of DCDMA involves a dominant HOMO-LUMO excited configuration. The characteristic feature of the excitation spectrum of DCDMA is the presence of progressions in the low-frequency mode, 112 cm^–1. The calculations suggest that this mode and some other active modes involve motions of the amino group and strongly interacting adjacent cyano substituents.     

Investigation of the tautomerism of nucleic acid bases by electronic-vibrational spectroscopy

Some problems on the tautomerism of nucleic acid bases have been studied by theoretical vibronic spectroscopy. Structural-dynamic models of molecules in excited states have been constructed. Based on the analysis of the change in the geometry of a pair of nucleic bases (adenine-thymine) upon electronic excitation, one possible reason for the formation of rare tautomeric forms is considered. The vibrational structure of the absorption spectra of purine and adenine tautomers has been calculated. The possibility of identifying the tautomeric forms of purine and adenine for different phase states with the aid of electronic-vibrational spectra is shown.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 703–711, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Microwave and low-frequency vibrational spectra of bullvalene

The microwave spectrum of bullvalene has been investigated in the region 18–40 GHz. In addition to transitions in the ground vibrational state, transitions arising from five excited vibrational states below 600 cm⁻¹ have also been observed. A combination of microwave intensity measurements and infrared and Raman data has been utilized to assign these vibrations. Three of the vibrations are E-type modes at 241, 355, and 588 cm⁻¹. One is an A₁-type mode at 445 cm⁻¹, and another is an A₂-type at 266 cm⁻¹. The microwave spectrum indicates the presence of a first-order Coriolis interaction for the E modes at 241 and 588 cm⁻¹. The first-order Coriolis coupling constant q = 0.557 MHz for the 241 cm⁻¹ vibration. The spectral results are consistent with C_3v symmetry for bullvalene.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

H2S : First Observation of the (70,0) Local Mode Pair and Updated Global Effective Vibrational Hamiltonian

The absorption spectrum of H₂S has been recorded by intracavity laser absorption spectroscopy in the spectral region 16 180–16 440 cm⁻¹ corresponding to an excitation of the (70^±, 0) local mode pair. Seventy-seven sublevels could be rotationally assigned and fitted with a rms of 0.009 cm⁻¹ by considering the (70^±, 0) local mode pair as isolated. The corresponding vibrational terms combined with all the levels reported in the literature were used to refine the effective vibrational Hamiltonian parameters of H₂³²S. The importance of the Fermi-type interaction is discussed.     

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.     

Phosphorescence spectra of acenaphthene,diphenyl, and carbazole

These spectra are for liquid-nitrogen temperature, the solvents being n-pentane, n-hexane, n-heptane, and n-octane. Each has a vibrational structure, the vibrational frequencies being independent of the solvent. Acenaphthene in pentane and octane gives 12 peaks corresponding to vibrational frequencies of 414, 630, 1152, 1409, and 1604 cm^–1, the last two being the strongest. Diphenyl in pentane and heptane gives gives 21 peaks; the strongest vibrations are 1610 and 1275 cm^–1, others being 1003, 320, and 735 cm^–1. Carbazole in pentane and hexane gives 15 peaks that fit the frequencies 750, 852, 1141, 1305, 1477, and 1605 cm^–1, the first and last being the strongest.     

Electronic spectrum of cobalt doped rubidium zinc sulphate hexahydrate

Optical absorption spectrum of Co²⁺ doped rubidium zinc sulphate hexahydrate has been investigated both at room and at liquid nitrogen temperatures. The gross features of the observed spectrum are characteristic of octahedral symmetry associated with spin-orbit interaction. The interelectronic repulsion (B, C), crystal field (Dq) and spin-orbit () parameters which give a good fit to the observed band positions areB = 860 cm^–1,C = 3870 cm^–,Dq = 980 cm^–1,= 500 cm^–1. The non-ligand bands observed in the spectrum are attributed to vibrational modes of water molecule.The authors are thankful to the Council of Scientific and Industrial Research, New Delhi (India) for financial support.     

Fluence and wavelength dependence of the IRMPA and IRMPD of CDCl3 with a CO2 laser

A TEA CO₂ laser was used to study the infrared multiple-photon absorption (IRMPA) and dissociation (IRMPD) spectra of CDCl₃ in the fluence ranges 0.01–1.4 and 7–45 J/cm², respectively, for different sample pressures. Experimental results were modeled with a master equation formulation which includes rotational and anharmonic bottlenecks and collisional effects. Experimental and calculated results show that CDCl₃ has great rotational and anharmonic restrictions at the first stages of excitation. The IRMPD spectrum falls more slowly than the linear absorption spectrum at the blue wing due to intramolecular vibrational relaxation at the quasi-continuum level of excitation.     

Evolution of the homogeneous IR spectrum of a highly vibrationally excited molecule as a result of a change in its vibrational energy

Using a photodissociation technique, we have measured the IR spectrum of thev ₂₁ mode of the (CF₃)₃ CI molecule with a vibrational energy ofE ₂=42500±3500 cm^–1 which is more than two times the dissociation energy. The experimental spectrum of a Lorenzian shape with a halfwidth of ₂=10.8±1.5 cm^-1 has been analyzed simultaneously with the results of the preceding work (₁=8.6±0.6 cm^-1) that were obtained at a lower vibrational energy (E ₁=36500±2500 cm^–1).     

Optical studies on free-standing polypyrrole films by the photopyroelectric method

Optical spectra of free-standing polypyrrole films were investigated by a novel PhotoPyroElectric (PPE) method. The reflection and absorption spectra in the range 2000–25000 cm^–1 of TsO^–- and ClO ₄ ^su– -doped polypyrrole films were obtained with an experimental setup comprising two pyroelectric sensors. The absorption bands due to electronic transitions to the bonding and antibonding bipolaronic levels appear at 11 000 and 21 500 cm^–1, respectively. Some relevant details in the polypyrrole spectrum in the 2000–5000 cm^–1 range were observed. The absorption band located at 3400 cm^–1 is characteristic for NH stretching vibration. The bands in the 2300–2500 cm^–1 range are ascribed to the vibration of N⁺H groups containing positively charged nitrogen. The PPE spectra also reveal changes of the electronic and vibrational absorption bands after polymer reduction and HCl treatment.     

Calculation and investigation of infrared absorption spectrum of rhodanine

The IR absorption spectrum of rhodanine was obtained in the 400–3500 cm^–1 region. A full set of frequencies for the vibrational spectrum was determined by a mechanical model with C_s symmetry, and an interpretation of the bands in the IR spectrum of rhodanine is given. The change in the IR spectrum of cyclopentane when the structure of the ring is complicated by introduction of two heteroatoms is examined. It is shown that a sulfur atom reduces and a nitrogen atom increases the frequencies of the ring stretching vibrations. Successive increase in the number of heteroatoms in the cyclopentane ring lowers the D_5h symmetry of the molecule, but traces of high symmetry remain in the spectrum of rhodanine.     

Fourier transform emission spectroscopy of the TiF radical in the 407 nm region

Ultraviolet emission spectra of the TiF radical in the 407 nm region have been observed at a resolution of 0.04 cm⁻¹ using a Fourier transform spectrometer. A new electronic assignment of ⁴Γ–X⁴Φ has been proposed. Rotational analysis has been obtained for the 0–0 and 1–1 vibrational bands of the ⁴Γ_5/2–X⁴Φ_3/2, ⁴Γ_9/2–X⁴Φ_7/2, and ⁴Γ_11/2–X⁴Φ_9/2 subbands and the 0–0 band of ⁴Γ_7/2–X⁴Φ_5/2. The lower state rotational and centrifugal distortion constants are consistent with the previous results [J. Mol. Spectrosc. 184 (1997) 186; J. Chem. Phys. 119 (2003) 9496], to the conformation that the lower state of the 407 nm band is the ⁴Φ ground electronic state. Rough estimates of the vibrational interval ΔG(1/2) and the spin–orbit coupling constant A in the ⁴Γ state were also obtained.     

The rotational spectrum of acrylonitrile in excited states of the two low-frequency CCN bending vibrational modes

The strongest vibrational satellites in the rotational spectrum of acrylonitrile have been assigned and frequencies of μ_a- and μ_b-type transitions in the frequency range 27–184 GHz are reported for the first two excited states in the lowest frequency in-plane CCN bending vibrational mode and the first excited state in the out-of-plane CCN bending mode. The values of the rotational constants, the quartic and sextic centrifugal distortion constants, and one octic centrifugal distortion constant are determined for each of these states. Less extensive results are also presented for the third quantum of the in-plane bend. The data set for the ground state has been extended by a number of new measurements and the improved ground state constants are used in a discussion of changes in rotational and centrifugal distortion constants with vibrational state where all constants associated with P_zⁿ and P²P_z⁽ⁿ⁻²⁾ terms in the Hamiltonian are found to reflect the common origin of the two CCN bends.     

Calculation and study of the IR absorption spectrum of hydantoin

The IR absorption spectrum of hydantoin has been obtained in the range 400–3500 cm^–1, and the normal-vibration frequencies are calculated on the basis of the mechanical model. The spectrum is interpreted.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol. 12, No. 6, pp. 116–120, June, 1969.     

Application of the method of energy moments to an analysis of the rotational and centrifugal constants of the H2O molecule

A method is described to compute the centrifugal constants from the first and second order energy moments. Presented as an illustration is a computation of the centrifugal constants of the H₂O molecule for the 000 vibrational state; conditions proposed in [2] were imposed on the parameters of the unitary transformation; the centrifugal constants obtained under such conditions reproduce the spectrum to 0.1 cm^–1 accuracy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 80–84, August, 1973.     

Role of Intermolecular Interactions in Forming the Vibrational Spectra of Carbohydrate Nitrate Crystals in the Region 1600–1700 cm−1

To elucidate the role of intermolecular interactions in forming the vibrational spectra of the crystals of carbohydrate nitrates in the region 1600–1700 cm^–1, theoretical calculations are performed (in the approximation of an additive model of interatomic interactions with the use of the Green's functions) for the density of vibrational states and the intensity of absorption bands in the IR spectrum of a methyl--D-glucopyranoside tetranitrate molecule in a crystal. It is shown that the splitting of absorption bands in the IR spectral region under consideration relates to the crystal effect.     

Optical emission diagnostics of laser-induced plasma for diamond-like film deposition

Optical emission from a laser-induced plasma plume is recorded during KrF excimer laser ablation of graphite in a gas mixture of Ar and H₂ (3%) for deposition of diamond-like thin films. At sub-GW/cm² laser intensities the spectrum is dominated by the bands of C₂ and CN. From the band intensities, the vibrational temperatures of both radicals are calculated to be 12–15×10³ K, and their concentrations are estimated to be 5×10¹⁴ cm^–3 and 2×10¹⁴ cm^–3, respectively.