On the mechanism of the broadening of the proton vibrational IR band in weak hydrogen bonds. Double adiabatic approximation

It is proposed that broadening of the ν_s (AH) IR band is due to the ν_s (AH) and ν_σ (AH…B) mode coupling and to the stochastic variation of the equilibrium distance R_e (A…B) modulating the proton vibration. The R_e disordering variation is caused by a coupling of the ν_σ mode with the low frequency oscillators (ν_Q) of the medium and of the complex as such. Besides, the (ν_σ, ν_Q) and (ν_s, ν_σ) couplings cause a ν_s frequency shift. Both the band broadening and the frequency shift increase with higher force constants responsible for (ν_σ, ν_Q) mode coupling. Furthermore the Q_i low frequency stochastic vibrations directly modulate the ν_σ (AH…B) vibration and the free AH groups stretching vibration (ν^o_s) causing some broadening at their bands which is however several times smaller than the ν_s band broadening in the complex. Several examples are reported to confirm the proposed model.     

LiC分子基态及其低电子激发态的多参考组态相互作用方法研究

采用包含Davidson修正的多参考组态相互作用(MRCI+Q)方法结合6-311++G(3df,3pd)基组计算了LiC分子基态(X4Σ-)以及五个低电子激发态(a2Π,b2Δ,c2Σ-,d2Σ+,A4Π)的势能曲线.将得到的势能曲线拟合到Murrell-Sorbie解析势能函数形式,确定了对应态的平衡结构Re、谐振频率ωe和离解能De等光谱数据,计算值与仅有的几个其他结果进行了比较.通过求解核运动的薛定谔方程首次报道了LiC分子几个低电子态在J=0下的振动能级、转动惯量和六个离心畸变常数(Dν,Hν,Lν,Mν,Nν和Oν).     

Resonance Raman spectroscopic study for radial vibrational modes in ultra‐thin walled TiO2 nanotubes

The study reports the observation of radial vibrational modes in ultra‐thin walled anatase TiO₂ nanotube powders grown by rapid breakdown anodization technique using resonant Raman spectroscopic study. The as‐grown tubes in the anatase phase are around 2–5 nm in wall thickness, 15–18 nm in diameter and few microns in length. The E_{g(ν1,ν5,ν6)} phonon modes with molecular vibrations in the radial direction are predominant in the resonance Raman spectroscopy using 325 nm He–Cd excitation. Multi‐phonons including overtones and combinational modes of E_{g(ν1,ν5,ν6)} are abundantly observed. Fröhlich interaction owing to electron–phonon coupling in the resonance Raman spectroscopy of ultra‐thin wall nanotubes is responsible for the observation of radial vibrational modes. Finite size with large surface energy in these nanotubes energetically favor only one mode, B_1g(ν4) with unidirectional molecular vibrations in the parallel configuration out of the three Raman modes with molecular vibration normal to the radial modes. Enhanced specific heat with increasing temperatures in these nanotubes as compared to that reported for nanoparticles of similar diameter may possibly be related to the presence of the prominent radial mode along with other energetic phonon mode. The findings elucidate the understanding of total energy landscape for TiO₂ nanotubes. Copyright © 2015 John Wiley & Sons, Ltd.     

Rotation–torsion analysis of the Si2H6 infrared fundamental ν9, perturbed by excited torsional levels of the vibrational ground state

The lowest infrared active perpendicular fundamental ν₉ of disilane has been analysed on a Fourier transform spectrum between 320 and 430?cm^?1, at the spectral resolution of 0.0012?cm^?1. The rotation–torsion structure of this band is affected by x,y Coriolis interactions with excited torsional levels of the vibrational ground state, correlating with components of 3ν₄ and 4ν₄ in the high barrier limit. The interaction of ν₉ and 4ν₄, forbidden in the D_3d symmetry limit, is allowed between components of E torsional symmetry under the G₃₆(EM) extended molecular group, because of the large amplitude of the internal rotation motion. We could determine the values of the main vibration–rotation–torsion parameters of ν₉, interaction parameters, and the vibrational wavenumbers of the four torsional components of 3ν₄ and of the E_3d component of 4ν₄. The intrinsic torsional splitting of ν₉ is found to be smaller than in the ground vibrational state by 0.0066?cm^?1, in good agreement with our theoretical predictions. The possibility of observing the effects of D_3d-forbidden interactions in the spectra of ethane-like molecules is also discussed.     

High-resolution infrared study of 1,1-ethylene-D2 in the 2000- to 1200-cm−1 region

The infrared spectrum of H₂CCD₂ was investigated in the region 2000-1200 cm^?1 at a resolution of ～0.05 cm^?1. Complete analyses of four type-A bands are reported-the CC stretch, ν₂, the CH₂ deformation, ν₁₂, and the overtones of the CD₂ and CH₂ wagging fundamentals, 2ν₇ and 2ν₈. Localized perturbations are identified and taken into account in the analyses, enabling the perturbing vibrational levels to be located accurately and the interaction parameters to be determined. In the case of ν₁₂, Fermi resonance with 2ν₁₀ has a global effect, and causes a bandhead to be formed in the K_a subband series.     

CO2 laser saturation Stark spectra and global rovibrational analysis of the main isotopic species of carbonyl sulfide (OC34S,O13CS,and 18OCS)

Stark spectra of OC³⁴S, O¹³CS, and ¹⁸OCS have been recorded with an intracavity CO₂ laser spectrometer. The observed transitions are the 2ν₂ band and the associated hot bands from ν₂¹, ν₁, 2ν₂⁰, 2ν₂², ν₁ + ν₂¹, 3ν₂¹, and 3ν₂³. One line has also been observed in the 00⁰1 ← 02⁰0 band of OC³⁴S. For each isotopic species of OCS, a global weighted least-squares analysis has been applied simultaneously on all available zero-field and Stark data, yielding coherent sets of rovibrational and electrical molecular parameters. From the equilibrium rotational constants we have deduced an improved equilibrium structure for the OCS molecule.     

FTIR spectra and rovibrational analysis of parallel bands involving the ν1, ν2, and ν3 levels of natural and monoisotopic FClO3

Fourier Transform infrared spectra of gaseous natural FClO₃ and monoisotopic F³⁵ClO₃ have been recorded at 293 and 225 K with a resolution of 0.04 cm⁻¹. Rotational J structure and, in part, K structure were resolved for the parallel fundamentals, combination bands, and overtones ν₁, ν₂, ν₃, ν₁ + ν₂, ν₁ + ν₃, ν₂ + ν₃, 2ν₁, 2ν₂, and 2ν₃. Band origins ν₀, anharmonicity constants χ_ij, and vibration-rotation interaction constants α_i^A and α_i^B have been determined. For F³⁵ClO₃, ν₀ values are ν₁ = 1063.238(6), ν₂ = 716.814(6), and ν₃ = 549.877(3) cm⁻¹. No perturbation was found at the present level of accuracy.     

High-resolution infrared study on DCCI: harmonic force field of monoiodoacetylene

A high-resolution infrared spectrum of DCCI has been measured in the regions of the bands of 2ν₁, ν₁+ν₂, ν₂+ν₃, ν₂+ν₄, ν₂+ν₅, and ν₄+ν₅. Using these bands together with the spectra measured previously, the rovibrational states of 2ν₁, ν₁+ν₂, ν₁+ν₃, ν₁+ν₄, ν₁+ν₅, ν₁+2ν₅, ν₂+ν₃, ν₂+ν₄, ν₂+ν₅, ν₂+2ν₅, ν₃+ν₄, ν₄+ν₅, and ν₄+2ν₅ have been analyzed. Various l-type and Fermi resonances have been taken into account in the analysis. In addition, the weak Coriolis resonance between the levels υ₃=υ₄=1 and υ₄=2 has been considered. Accurate values for the molecular constants and the appropriate resonance parameters have been obtained. The unperturbed normal vibrational frequencies associated to the equilibrium state have been calculated for both isotopic species HCCI and DCCI. Then the harmonic force constants for monoiodoacetylene have been determined.     

The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands of 15NH3

The ir absorption of gaseous ¹⁵NH₃ between 510 and 3040 cm^?1 was recorded with a resolution of 0.06 cm^?1. The ν₂, 2ν₂, 3ν₂, ν₄, and ν₂ + ν₄ bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. ?pirko, J. M. R. Stone, and D. Papou?ek (J. Mol. Spectrosc.60, 159–178 (1976)). A set of effective molecular parameters for the ν₂ = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν₄ and ν₂ + ν₄ bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν₄ in ¹⁴NH₃ by ?. Urban et al. (J. Mol. Spectrosc.79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.     

Inversion-rotation interaction in NH2D: Intensity perturbations in the ν2 band

The parameters of NH₂D in the ground and ν₂ states have been refined by a simultaneous analysis of the microwave, FTIR, and diode laser data. The intensities of 46 NH₂D lines have been measured, and from a least-squares fit of the intensity data the a ← s, s ← a, s ← s, and a ← a transition moments have been derived. The intensities of the lines in the ν₂ band of NH₂D have been calculated taking into account the inversion-rotation interaction. The accuracies of the wavenumbers and intensities calculated with the new parameters are estimated to be better than ±0.0002 cm⁻¹ and ±5%, respectively. The matrix elements for interaction of vibrations through x, y, and z axis couplings are appended.     

High-Resolution Fourier-Transform Intracavity Laser Absorption Spectroscopy of D2O in the Region of the 4ν1+ν3 Band

The high-resolution absorption spectrum of the D₂O molecule was recorded with the Fourier-transform intracavity laser absorption spectrometer in the region 12 570-12 820 cm⁻¹ where the band 4ν₁+ν₃ is located. Transitions belonging to the 4ν₁+ν₃ band, and the bands 3ν₁+2ν₃ and 3ν₁+2ν₂+ν₃, of which the up states are strongly interacted with that of the 4ν₁+ν₃, were assigned in the recorded spectrum. Up state energy levels were fitted to derive effective spectroscopic parameters, which reproduce majority of the assigned transitions within the experimental accuracy.     

Subject index for volume 100

The ν₂ fundamental band of HNCO has been observed for the first time under a resolution of 0.015 cm^?1. The band origin for this NCO antisymmetric stretching vibration is found to be at 2268.893 cm^?1, rather distant from the previously reported value of 2274 cm^?1. Nineteen subbands have been analyzed and term values for both ground and ν₂ states with K up to 4 have been obtained. Effective rotational constants B and centrifugal distortion constants D and H have also been determined. Interactions are observed with 2ν₄ + ν₅ and ν₃ + ν₄. Large perturbations are observed for K = 0 and K = 1 levels of ν₂. Transitions are also seen for three other vibrations, ν₄ + ν₅ + ν₆, ν₃ + ν₆, and 2ν₄ + ν₆.     

The Raman spectrum of solid cyclopropane

The Raman spectrum of polycrystalline cyclopropane between 3200 and 10 cm^?1 has been recorded. All Raman active fundamentals, two other fundamentals ν₄(A″₁) and ν₇(A″₂), several new crystal components of fundamentals, and many new bands arising from overtones and combinations have been observed.The splittings of the fundamentals, together with the coincidences of infrared and Raman wavenumbers for both fundamentals and lattice modes, are consistent with a C_2v factor group, a C_s site, and two molecules per orthorhombic unit cell.     

The ν7 vibrational states of C3O2: A least-squares fit of the rigid-bender model to the v7ν7l7 energies and rotational constants

The rigid-bender model is used to treat the large-amplitude, low-frequency, bending vibration ν₇ of C₃O₂. Different parameterizations of the bending potential function are considered, and a simple two-term power series is found to give the best fit. With this parameterization, using a least-squares fit to energies and B values, the ν₇ potential function is determined for the ground state as well as for the states in which ν₂, ν₃, ν₄, ν₆, 2ν₆, ν₁ + ν₃, ν₁ + ν₄, ν₂ + ν₃, and 2ν₂ + ν₄ are excited. The excitation of other vibrations has in some cases a drastic effect on the ν₇ potential. In the ground state the potential has a 29 cm^?1 barrier at the linear position, in ν₁ + ν₃ the barrier increases to 79 cm^?1, while in 2ν₂ + ν₄ the barrier vanishes. An equilibrium potential is determined by correcting the ground state potential for the effects of zero-point motion of the normal vibrations ν₁, …, ν₆. This potential has a 35.6-cm^?1 barrier with a minimum at α = 11.14°, where 2α is the angular deviation from linearity. The model accurately predicts the quartic and sextic centrifugal distortion terms for the low-lying v₇ν₇^l₇ states. Second-order l-type coupling is included in the calculations of the quartic terms. The effects of this coupling, which are most pronounced for the ν₇ ≥ 2 states, adequately explain the negative D term recently reported for the ν₂ + 4ν₇⁰ state.     

Multispectrum analysis of CH4 from 4100 to 4635 cm: II. Air-broadening coefficients (widths and shifts)

Room temperature Lorentz air-broadened halfwidth and pressure-induced air-shift coefficients were measured for 1011 transitions in the octad region of methane between 4100 and 4635 cm⁻¹. These measurements were made by analyzing 10 laboratory absorption spectra recorded at 0.011 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 2.05 and 150 cm. The total sample pressures ranged from 99 to 400 torr with CH₄ volume mixing ratios of 0.01 in dry air. The spectral line parameters were retrieved using a multispectrum nonlinear least squares technique. Transitions belonging to five bands of the octad polyad were observed, namely ν₂ + 2ν₄, ν₁ + ν₄, ν₃ + ν₄, 2ν₂ + ν₄, and ν₂ + ν₃. The numbers of measurements by bands are: 33 for ν₂ + 2ν₄, 180 for ν₁ + ν₄, 635 for ν₃ + ν₄, 33 for 2ν₂ + ν₄, and 130 for ν₂ + ν₃. Transitions with rotational quantum number J up to 16 are included in the analysis. The measured width and shift coefficients vary according to the tetrahedral symmetry species and the rotational quantum numbers of the transitions. The retrieved parameters from this study are compared with prior results, in part to estimate absolute accuracy and determine the extent of vibrational dependence of widths and shifts.     

Experimental and theoretical studies of the vibrational spectra of CHD2Br

The dideuterated form of methyl bromide, CHD₂Br, has been synthesized and the gas-phase infrared spectra investigated in the range 400–10,000?cm^–1 using a medium-resolution FTIR spectrometer. The nine fundamental bands have been characterized in detail. Six of them, i.e. ν ₁, ν ₄, ν ₅, ν ₇, ν ₈ and ν ₉, have been rotationally analysed through the assignment of the partially resolved structure of the ^PQ_K and ^RQ_K cluster of lines and the spectroscopic parameters have been derived in the symmetric top limit approximation. Among the fundamental levels, anharmonic resonance occurs between ν ₇/ν ₄?+?ν ₈ and ν ₈/ν ₆?+?ν ₉. An isotopic ^79/81Br shift was found for ν ₆ and in the more complex region of the ν ₈ fundamental. High-quality ab initio calculations – carried out at coupled cluster level [CCSD(T)] employing the correlation-consistent basis set of Dunning (cc-pVTZ) – were performed to determine quadratic, cubic and quartic (semidiagonal) force constants. Using these constants and applying second-order vibrational perturbation theory (VPT2), with allowance for resonances (when necessary), permitted us to identify and assign, in addition to the fundamentals, about 70 overtones and combination bands up to three quanta.     

Absorption Spectrum of H2O in the Range 12 400-14 520 cm

Fourier transform spectra recorded using (a) natural abundance water vapor, (b) H₂¹⁸O-enriched water vapor, and (c) H₂¹⁷O-enriched water vapor are analyzed. The ratio of intensities in three spectra is used to identify 927 lines due to absorption by H₂¹⁸O. Intensities and self-broadening parameters are derived for these lines. Using theoretical linelists, comparisons with previously assigned H₂¹⁶O spectra, and automatic searches for combination differences, 747 lines are assigned. These lines belong to 14 vibrational states in the 3ν+δ and 4ν polyads. Newly determined H₂¹⁸O vibrational band origins include 4ν₁ at 13 793.09 cm⁻¹, 3ν₁+ν₃ at 13 795.40 cm⁻¹, 2ν₁+2ν₃ at 14 188.82 cm⁻¹, ν₁+3ν₃ at 14 276.34 cm⁻¹, and 2ν₂+2ν₂+ν₃ at 13 612.71 cm⁻¹. These results are compared with data in HITRAN.     

The ν2 + ν4 and 2ν2 isotropic Raman bands of 12CH4

The purely isotropic Raman spectrum of the ν₁ band, the ν₂ + ν₄ band (enhanced through interaction with ν₁), and the 2ν₂ band of ¹²CH₄ was obtained with a spectral resolution of 0.30–0.35 cm^?1 from exposures with different orientations of the linearly polarized exciting light. The ν₂ + ν₄ and 2ν₂ bands show partially resolved rotational structure. The spectra are interpreted in terms of a model which takes explicitly into account vibrational and rovibrational interactions with other vibrational states, using molecular constants determined primarily from infrared spectra. The computed contours are in excellent agreement with the experimental ones and the observed and calculated peak wavenumbers agree within one tenth of the spectral resolution limit, except for a small region near the ν₁ band. The good overall agreement represents an independent check on the overall correctness of the previously reported molecular constants. A detailed discussion is given of the contributions to the intensities of individual transitions from the three transition moment matrix elements, which in an isolated-band model are the intensity parameters of the ν₁, 2ν₄, and 2ν₂ isotropic bands, respectively.     

The ν4 band of CD3I with perturbations: A high-resolution infrared study

The infrared band ν₄ of CD₃I between 2220 and 2390 cm^?1 has been investigated at a resolution of 5.4 × 10^?3 cm^?1. More than 2000 lines were assigned to subbands with KΔK from ?18 to 21, including J values up to 70. In the analysis the Coriolis resonances with ν₃ + ν₅^±1 + ν₆^±1, ν₂ + 2ν₆^±2, ν₂ + 2ν₆⁰, and 2ν₃ + 2ν₆^±2 were taken into account. The molecular constants concerning the fundamental ν₄, as well as the parameters describing the combination levels, were derived.     

Laser Stark spectroscopy of methyl cyanide in the 10-μm region: Analysis of the ν4 and ν7 bands,and the ν7, 3ν81 interaction

About 550 Stark tuned resonances of the ν₄ and ν₇ vibration-rotation bands of CH₃CN were measured using ¹²CO₂, ¹³CO₂, and N₂O lasers. These data are combined with 26 microwave measurements and fitted to a model which includes l-type doubling in ν₇, ν₄-ν₇ Coriolis coupling, and ν₇-³ν₈¹ Coriolis and Fermi couplings. The infrared and microwave data can be reproduced with standard deviations of 7 MHz and 40 kHz, respectively. The many vibration-rotation parameters and the dipole moments are determined with great accuracy. A complete list of derived parameters is given in Table I.