Effect of collision-induced phase-shifts on the line widths and line shifts of CO2-Ar system

The theoretical calculation of line widths and line shifts for CO₂-Ar system is computed by the Mehrotra-Boggs theory. It is shown for this system that the phase shift effect is very important at large values of |m| wherem is the value of rotational quantum numberJ in the lower vibrational state. It is also pointed out that the Salesky-Korff theory is the same as the Mehrotra-Boggs theory.     

Experimental and theoretical studies of room-temperature sub-millimetre CH3 35Cl line shapes broadened by H2

Hydrogen-broadening coefficients of methyl chloride rotational lines J?=?6?→?7, 10?→?11, 17?→?18, 22?→?23 and 31?→?32 at 296?K are measured as functions of the quantum number K using a sensitive frequency-modulation technique. As expected for this light perturber, the observed line shapes are well described by Voigt profile model. A clear dependence of the collisional broadening on K is observed for most transitions. From a detailed study of the K-components of the transition J?=?6?→?7 situated at 186?GHz no variation of the broadening of the hyperfine components related to ³⁵Cl quadrupole is stated. Given the absence of refined ab initio computed potential energy surfaces and the impracticality of quantum-mechanical calculations for the considered molecular system, theoretical values of these broadening coefficients are estimated by a semi-classical approach with exact trajectories and a model interaction potential including both long-range and short-range (atom-atom) interactions of the active molecule rigorously treated as a symmetric top. It is shown that the short-range forces yield important contributions to the collisional line width for all values of the rotational quantum numbers J and K. Various models are also tested for the isotropic part of the interaction potential which governs the relative translational motion. It is demonstrated that for the very light perturbing molecule H₂ the calculated line widths, practically independent from the rotational quantum number J (for K?≤?J), are particularly sensitive to the position and slope of the repulsive wall. Modifications required in the semi-classical formalism for a correct application of the cumulant expansion are also tested and it is stated that no difference is observed for the CH₃Cl–H₂ system characterised by quite weak interactions.     

The pure rotational spectra of the two lowest energy conformers of the asymmetric ether C4H9OC2H5

An experimental study has been performed shedding light on the conformational energies of the asymmetric ether n-butyl ethyl ether. Rotational spectroscopy between 7.8 GHz and 16.2 GHz has identified two conformers of n-butyl ethyl ether, C₄H₉OC₂H₅. In these experiments spectra were observed as the target compound participated in an argon expansion from high to low pressure causing molecular rotational temperatures to be below 4 K. For one conformer, 95 pure rotational transitions have been recorded, for the second conformer, 20 pure rotational transitions were recorded. Rotational constants and centrifugal distortion constants are presented for both butyl ethyl ether conformers. The structures of both conformers have been identified by exploring the multi-dimensional molecular potential energy surface using ab initio calculations. From the numerous low energy conformers identified using ab initio methods, the three lowest conformers were pursued at increasingly higher levels of theory, i.e. complete basis set extrapolations, coupled cluster methods, and also taking into consideration zero point vibrational energies. The two conformers observed experimentally are only revealed to be the two lowest energy conformers when high levels of quantum chemical methodologies are employed.     

The rotational Raman spectra and cross sections of H2O, D2O, and HDO

We report the experimental rotational Raman spectra of H₂O, and of a mixture of D₂O and HDO in the vapor phase at room temperature, and their interpretation in terms of rotational–vibrational energies, wavefunctions, and transition moments of the molecular polarizability. These transition moments are based on high-level ab initio calculations of the wavelength dependent polarizability surface, and on wavefunctions where the rotational–vibrational coupling is considered in detail. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the rotational Raman spectra can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

A new study of the ν 2(A 1) infrared band of phosphorus trifluoride

The high-resolution Fourier transform infrared spectrum of phosphorus trifluoride (PF₃) has been reinvestigated in the v_2?=?1 vibrational excited state near 487?cm^?1 (at a resolution of 3?×?10^–3?cm^–1). Thanks to our new accurate rotational ground-state C ₀ value, 0.159970436(69)?cm^–1, and to recent pure rotational measurements, 318 new infrared transitions of the ν ₂ fundamental band have been assigned, extending the rotational quantum number values up to K _max?=?71 and J _max?=?72. A merge, for the first time, of 135 reported microwave data (K _max?=?42 and J _max?=?49) within the v_2?=?1 excited level and 2860 rovibrational transitions yielded improved constants of ν ₂. Parameters of this band have been obtained, up to sextic centrifugal distortion constants, by least-squares fits, σ _IR?=?3.60?×?10^–4?cm^–1 and σ _MW?=?5.53?×?10^–6?cm^–1 (166?kHz). Comparison of these constants with those measured previously by infrared spectroscopy reveals orders of magnitude higher accuracy of these new values.     

A comprehensive model to predict the microwave spectrum of propyne in the region 17–70 GHz for the ground and v10 = 1, 2, 3, 4, 5 vibrational states

A comprehensive model for predicting rotational frequency components in various v₁₀ vibrational levels of propyne was developed. A number of components of the rotational spectra in the ground and v₁₀ = 1, 2, 3, 4 excited vibrational states of propyne in the frequency range 17–70 GHz have been obtained. Molecular constants for these vibrationally excited states have been determined from more than 100 observed rotational transitions. From these experimentally observed components and a model based upon first principals for C_3v molecules, rotational constants have been expressed in a form which enables one to predict rotational components for vibrational levels for propyne up to v₁₀ = 5. The model also appears to be useful in predicting rotational components in more highly excited vibrational levels but data were not available for comparison with the theory. Experimentally measured frequencies are presented and compared with those calculated using the results of basic perturbation theory.     

Einstein A-coefficients for rotational transitions in the HN2O+

EinsteinA-values for the electric dipole transitions between the rotational levels up to 540 cm⁻¹ andJ=11 in the ground vibrational state of the protonated N₂O (i.e., HN₂O⁺) are calculated. The coefficients are used to compute the mean radiative lifetimes of the levels. TheseA-values can be used for analysing the spectra from astronomical objects, if observed.     

Fourier-transform microwave and submillimeter-wave spectroscopy of chloroiodomethane, CH2ICl

Guided by a previous microwave study (9–35 GHz), the rotational spectrum of both chlorine isotopologues of chloroiodomethane in its vibrational and electronic ground state has been re-investigated in the microwave region and extended to the millimeter/submillimeter-wave region. Weak a-type transitions have been recorded by Fourier transform microwave spectroscopy below 20 GHz whilst strong b-type rotational transitions have been recorded between 15 and 646 GHz, corresponding to energy levels with J″ ≤ 108 and . Molecular constants including those describing the hyperfine structures owing to the two halogen atoms were accurately determined for both species from the least-squares analysis of a total of 1475 distinct transition frequencies (of which 906 belong to the CH₂I³⁵Cl isotopologue). The two sets of rotational constants allowed us to derive an r₀ structure of CH₂ICl.     

The infrared spectrum of 13C2H2 in the 60–2600 cm−1 region: bending states up to v 4 + v 5 = 4

The vibration–rotation spectra of ¹³C substituted acetylene, ¹³C₂H₂, have been recorded in the region between 60 and 2600?cm^?1 at an effective resolution ranging from 0.001 to 0.006?cm^?1. Three different instruments were used to collect the experimental data in the extended spectral interval investigated. In total 9529 rotation vibration transitions have been assigned to 101 bands involving the bending states up to v _tot?=?v ₄?+?v ₅?=?4, allowing the characterization of the ground state and of 33 vibrationally excited states. All the bands involving states up to v _tot?=?3 have been analyzed simultaneously by adopting a model Hamiltonian which takes into account the vibration and rotation l-type resonances. The derived spectroscopic parameters reproduce the transition wavenumbers with a RMS value of the order of the experimental uncertainty. Using the same model, larger discrepancies between observed and calculated values have been obtained for transitions involving states with v _tot?=?4. These could be satisfactorily reproduced only by adopting a set of effective constants for each vibrational manifold, in addition to the previously determined parameters, which were constrained in the analysis.     

Rotation-vibration energy cluster formation in XH2D and XHD2 molecules (X = Bi, P, and Sb)

We investigate theoretically the energy cluster formation in highly excited rotational states of several pyramidal XH₂D and XHD₂ molecules (X = Bi, P, and Sb) by calculating, in a variational approach, the rotational energy levels in the vibrational ground states of these species for J?70. We show that at high J the calculated energy levels of the di-deuterated species XHD₂ exhibit distinct fourfold cluster patterns highly similar to those observed for H₂X molecules. We conclude from eigenfunction analysis that in the energy cluster states, the XHD₂ molecule rotates about a so-called localization axis which is approximately parallel to one of the X-D bonds. For the mono-deuterated XH₂D isotopologues, the rotational spectra are found to have a simple rigid-rotor structure with twofold clusters.     

Dynamics of a Loss-Modulated, Two-Wave CO2 Laser Lasing on Lines of Different Vibrational Bands

The nonlinear dynamics of a loss-modulated, two-wave CO₂ laser lasing on vibrational–rotational lines of different vibrational bands has been investigated theoretically and experimentally. It is shown that the time and energy parameters of laser radiation can be controlled within fairly wide limits by changing the depth and frequency of modulation and the ratio between the constant components of the losses.     

Line broadening,shifting and mixing parameters for the ν1 + ν3 band of OCS perturbed by N2 and O2

In this paper, we report measured Rosenkranz N₂- and O₂-broadening, induced pressure-shift and mixing coefficients for OCS in the ν₁ + ν₃ band, using a multi-pressure fitting technique applied to the measured shapes of the lines, including the interference effects caused by the line overlaps. These measurements were made by analysing six laboratory absorption spectra recorded at 0.004 cm^?1 resolution using the Fourier transform spectrometer Bruker IFS125HR located at the Laboratoire Interuniversitaire des Systèmes Atmosphériques, in Créteil. The spectra have been recorded in the 1850–3000 cm^?1 wave number range at 295 K, using a multipass absorption cell with an optical path of 3.249 m. The total sample pressures ranged from 5.97 to 83.28 Torr with OCS volume mixing ratios between 0.001 and 0.013 in nitrogen or oxygen. We have been able to determine the N₂- and O₂-pressure-broadening coefficients of 81 ν₁ + ν₃ transitions with rotational quantum number J up to 50. The measured N₂- and O₂-broadening coefficients range from 0.0815 ± 0.0698 to 0.1169 ± 0.1027 cm^?1 atm^?1 at 295 K, respectively. Most of the measured pressure shifts are positive. The reported N₂- and O₂-induced pressure-shift coefficients vary from about ?0.0103 ± 0.0092 to 0.0097 ± 0.0092 cm^?1 atm^?1, respectively. We have examined the dependence of the measured broadening parameters on the quantum number m (m = ?J for the P branch and m = J + 1 for the R branch) and also developed an empirical expression to describe the broadening coefficients in terms of |m|. On average, this empirical expression reproduces the measured broadening coefficients to within 2%. Using a semi-classical Robert and Bonamy formalism, the theoretical broadening coefficients have been calculated at room temperature and compared with the experimental results. The theoretical results of the broadening coefficients are in very good overall agreement with the experimental data (2%).     

Vibrational and Rotational Spectroscopy of 13CD3OD

We have used Fourier Transform spectral data on the C-O stretching mode of ¹³CD₃OD in order to perform a vibro-rotational analysis for this molecule. We have estimated a few molecular parameters of the ground and C-O stretching vibrational modes. Based on these parameters, and by using the Kwan-Dennison model, we propose assignments for a number of far-infrared laser transitions of ¹³CD₃OD.     

N2O+离子A2Σ+电子态高振动能级的转动结构分析

利用一束波长为36055nm的激光,通过(3+1)共振多光子电离方法制备纯净的且处于X²Π_1/2,3/2(000)态的N₂O⁺离子,用另一束激光激发所制备的离子到第一电子激发态A²Σ⁺的不同振动能级,然后解离,通过检测解离碎片NO⁺强度随光解光波长的变化,得到了转动分辨的N₂ 关键词： 2O⁺离子A²Σ⁺电子态')" href="#">N₂O⁺离子A²Σ⁺电子态 共振增强多光子电离 光解碎片激发光谱 光谱常数     

The lowest frequency vibrational fundamental of disilane: A three-band analysis

The lowest frequency perpendicular fundamental band ν₉ of disilane has been analyzed to investigate torsion mediated vibrational interactions. We report here a three-band analysis involving torsional levels built on the ground state, the ν₉ vibrational fundamental, and ν₃ fundamental. This analysis includes transitions from the far-infrared torsional bands, ν₄, 2ν₄ − ν₄, 3ν₄ − 2ν₄, two perturbation-allowed rotational series from the overtone band 3ν₄ and transitions restricted to −21 ? kΔk ? 21 in the ν₉ fundamental band. An excellent fit to the included data was obtained. Two interactions are identified in this fit, a resonant Coriolis interaction between the ν₉ torsional stack and that of the ground vibrational state and a Fermi interaction between the ν₃ fundamental and the gs. The introduction of the Fermi interaction causes a large change in the barrier height for the ground vibrational state and makes the barrier shape parameter redundant, indicating that the vibrational contributions to the experimental barrier shape are dominant. Such effects have also been observed for ethane and other similar molecules.     

Pressure Shifts and Pressure Broadening of the B and γ Bands of Oxygen

Measurements of pressure shift and pressure broadening in molecular oxygen have been made for rotational transitions in the B (1←0) and γ (2←0) vibrational bands of the b¹Σ⁺_g←X³Σ⁻_g visible electronic transition. The absorption features were measured simultaneously in two cells by photoacoustic spectroscopy using a scanning dye laser. The measurements were made with background gases of both pure oxygen and air at room temperature. The pressure shifts were all negative. The measurements show the magnitude of the pressure shift increasing with vibrational quantum number when compared with existing data for the A (0←0) band. The shifts also increase with rotational number within each vibrational band. The shifts in air are larger than in oxygen although the difference gets smaller with vibrational number. The average shifts in air for the A, B, and γ bands were 36, 11, and 0.2% higher, respectively, than in pure oxygen. The pressure broadening of the rotational lines does not change significantly with vibrational number and in general decreases with rotational number within a band. The pressure shift measurements were used by the high-resolution Doppler imager (on the Upper Atmospheric Research Satellite) to correct the Doppler wind measurements.     

Reinvestigation of the second negative (A 2 Π u−X 2 Π g) band system of O 2 +

TheA ² Π _ustate of O₂ ⁺ was earlier established as an inverted state contrary to previous assumptions. The rotational analysis of a few more bands of theA-X system of O₂ ⁺ has now been completed. These studies show that the spin-orbit coupling constantA in theA ² Π _ustate gradually varies with the vibrational quantum numberν and is found to be positive forν⩾6. It has also been observed that the spia-rotation interaction is not negligible in theA ² Π _ustate. The spin splitting constantγ is reported for various vibrational levels of this electronic state.     

Formaldehyde around 3.5 and 5.7-μm: Measurement and calculation of broadening coefficients

Self- and N₂-broadening coefficients of H₂CO have been retrieved in both the 3.5 and 5.7-μm spectral regions. These coefficients have been measured in FT spectra for transitions with various J (from 0 to 25) and K values (from 0 to 10), showing a clear dependence with both rotational quantum numbers J and K. First, an empirical model is presented to reproduce the rotational dependence of the measured self- and N₂-broadening coefficients. Then, calculations of N₂-broadening of H₂CO were made for some for 3296 ν₂ transitions using the semi-classical Robert-Bonamy formalism. These calculations have been done for various temperatures in order to obtain the temperature dependence of the line widths. Finally, self- and N₂-broadening coefficients, as well as temperature dependence of the N₂-widths has been generated to complete the whole HITRAN 2008 version of formaldehyde (available as supplementary materials).     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^–1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387–400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.     

The infrared spectrum of NH3-dn trapped in solid neon

The infrared spectra of normal and deuterium-enriched Ne:NH₃=1600:1 deposits at 4.3 K have been observed, and the structure associated with almost all of the vibrational fundamentals has been assigned. Although the most prominent absorptions arise from the ground-state J=0 level(s), incomplete nuclear-spin equilibration enhances the contribution of absorptions arising from the ground-state J=1 levels. As had been proposed in an earlier study, the inversion splitting for the ν₂ fundamental is appreciably reduced from that observed for the gas-phase molecule, and the rotational structure associated with the J=1 levels of the vibrationally excited molecule is somewhat perturbed. Ammonia is trapped in two different types of site in solid neon. Matrix shifts from the corresponding gas-phase absorptions amount to only a few cm⁻¹, and are smaller than those previously reported for ammonia trapped in an argon matrix.