Analysis of the high resolution spectrum of the fundamental bandsv2 andv5 of12CH3F and their interactions

Thev ₂(A₁) andv ⁵(E) fundamental vibration-rotation bands of¹²CH₃F have been recorded under high resolution (0.015 to 0.020 cm^–1) in the spectral range of 1460 cm^–1. About 1100 transitions have been assigned. The Coriolis interaction between v₂=1 and v₅=1, and the l(2,-1) interaction in v₅=1 have been rigorously treated. Sixteen molecular constants have been determined from a least squares analysis. They reproduce the observed data with an overall standard deviation of 0.0037 cm^–1.     

Study of processes of translational,rotational, and vibrational relaxation based on CARS spectra line shapes

This paper reviews the various physico-chemical processes responsible for actual linewidths encountered in high-resolution coherent anti-Stokes Raman spectroscopy (CARS). Most of the experimental data are based on linewidth measurements using a pulseamplified CARS spectrometer with an emission bandwidth (FWHM) of 2×10^–3 cm^–1. Detailed rotational and vibrational relaxation constants have been obtained from the analysis of theQ-branch profiles of C₂H₂, N₂, CH₄, and SiH₄.     

The ν1 and ν3 stretching fundamental bands of PD3

The infrared (IR) spectrum of PD₃ has been recorded in the 1580–1800 cm⁻¹ range at a resolution of 0.0027 cm⁻¹. About 2400 rovibrational transitions with J^′=K^′22 have been measured and assigned to the ν₁ (A₁) and ν₃ (E) stretching fundamentals. These include 506 “perturbation-allowed” transitions with selection rules Δ(k−l)=±3. Splittings of the K^′′=3 lines have been observed. Effects of strong perturbations are evident in the spectrum. Therefore the rovibrational Hamiltonian adopted for the analysis explicitly takes into account the Coriolis and k-type interactions between the v₁=1 and v₃=1 states, and includes also several essential resonances within these states. The rotational structure in the v₁=1 and v₃=1 vibrational states up to J^′=K^′=18 was reproduced by fitting simultaneously all experimental data. Thirty-four parameters reproduced 1950 transitions retained in the final cycle with a standard deviation of the fit equal to 4.9 × 10⁻⁴ cm⁻¹ (about the precision of the experimental measurements).     

High-resolution infrared and millimeterwave spectra of the v3=1 vibrational state of NF3 at 907 cm

The ν₃^±1 perpendicular band of ¹⁴NF₃ ( cm⁻¹) has been studied with a resolution of 2.5 × 10⁻³ cm⁻¹, and 3682 infrared (IR) transitions (J_max=55, K_max=45) have been assigned. These transitions were complemented by 183 millimeterwave (MMW) rotational lines (J_max=25, K_max=19) in the 150–550 GHz region (precision 50–100 kHz). The kl=+1 level reveals a strong A₁/A₂ splitting due to the l(2,2) rotational interaction (q=−4.05 × 10⁻³ cm⁻¹) while the kl=−2 and +4 levels exhibit small A₁/A₂ splittings due to l(2,−4) and l(0,6) rotational interactions. All these splittings were observed by both experimental methods. Assuming the v₃=1 vibrational state as isolated, a Hamiltonian model of interactions in the D reduction, with l(2,−1) rotational interaction (r=−1.96 × 10⁻⁴ cm⁻¹) added, accounted for the observations. A set of 26 molecular constants reproduced the IR observations with σ_IR=0.175 × 10⁻³ cm⁻¹ and the MMW data with σ_MMW=134 kHz. The Q reduction was also performed and found of comparable quality while the QD reduction behaved poorly. This may be explained by a predicted Coriolis interaction between v₃=1 and v₁=1 (A₁, 1032.001 cm⁻¹) which induces a slow convergence of the Hamiltonian in the QD reduction but has no major influence on the other reductions. The experimental equilibrium structure could be calculated as: r_e(N–F)=1.3676 Å and (FNF)=101.84°.     

Determination of the isotopic composition of hydrogentritium mixtures by emission spectroscopy

Absolute effective cross sections for collisions of the second kind are evaluated by studying the dependence of line or molecular band intensification on the partial pressures of mixture components in a glow discharge. Determination of the cross sections is based on measurement of the relative intensities of the corresponding bands in mixtures of different percentage composition. The resulting values for the effective cross sections Q are as follows: N₂(C³ II)_v=3 and Ar(³P_o) 3.10^–15 cm², N₂(C³ II)_v=2 and Ar(³P₂) 0.8.10^–15 cm, N₂(C³ II)_v=0 and CO 2.10^–15 cm, CO(C³ II)_v=0 and Ar(³P₂) 0.3.10^–15 cm².In conclusion, the authors wish to thank V. S. Mel'chenko for discussing the results of the present study.     

Temperature dependence of the quenching of N<Subscript>2</Subscript> (C <Superscript>3</Superscript>Π<Subscript>u</Subscript>) by N<Subscript>2</Subscript> (X) and O<Subscript>2</Subscript> (X)

The temperature dependences of the quenching rate constants of the states N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}}${\rm C} \ {^{3}{ \rm \Pi }_{u}} v^′=0,1) by N₂ (X) and of the state N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0) by O₂ (X) are studied. Time-resolved light emission from the gas was analyzed in the temperature range from 300 K to 210 K keeping the gas at constant density. In case of quenching by N₂ (X), the quenching rate constant for the vibrational level v^′= 0 increases by (13 ±3)% with gas cooling whereas the quenching rate constant for v^′= 1 decreases by (5.0 ±2.5)% in this temperature range. For quenching by O₂ (X), the quenching rate constant decreases by (3 ±2)% with gas cooling. The temperature variation of the N₂ (C ³Π_u v^′=0) emission intensity for pure nitrogen and dry air are calculated using the obtained quenching rate constants and is compared with the experimental data available in the literature.     

Degenerate four-wave-mixing spectroscopy in NaH

We performed DFWM spectroscopy on X ^–1+–A ¹⁺ transitions in NaH produced in an indirect photochemical reaction between Na(3p) and H₂ and detected v=1, 2 and 3 ground state vibrational levels of NaH molecules, whereas with resonance enhanced CARS, we observed v=0 levels only. This different sensitivity can be explained by considering the Franck-Condon-factors and the relevant damping coefficients for the corresponding transitions in the NaH molecule. Time resolved DFWM spectroscopy showed that NaH(v=1) molecules effectively live much longer than Na(3p) atoms which merely follow the laser excitation pulse.     

Vibrational Analysis of Coherent Anti-Stokes Resonance Raman Spectra from Bacteriorhodopsin Containing Isotopically Substituted Retinal Chromophores

Vibrational spectra recorded by coherent anti-Stokes resonance Raman scattering (CARS) from bacteriorhodopsin (BR) samples containing isotopically substituted (²H and ¹³C) retinal chromophores were measured using high repetition rate, low-power, picosecond pulsed excitation (λ₁=580 nm and λ_s=640±3 nm). These picosecond resonance CARS (PR/CARS) data were analyzed via third-order susceptibility relationships [χ ^{( 3 )} ] to obtain band origins, bandwidths, relative intensities, and electronic phase factors assignable to all significant vibrational Raman features in the 1490–1700 cm⁻¹ wavenumber region (the ethylenic stretching and C = N–H rocking or Schiff base modes). Isotopic substitution selectively places ²H at C₁₅, ¹³C singly at the C₁₀ position and at the C₁₄ position, and ¹³C simultaneously in positions of C₁₄ and C₁₅. Each isotopic BR sample was examined not only in H₂O, but also in D₂O, which places a ²H at the Schiff base nitrogen of the retinal. In addition, PR/CARS data were recorded from each isotopic BR sample following either light adaptation [i.e. the BR sample contained a single retinal isomer (all- trans , 15- anti or BR-570)] or dark adaptation [i.e. the BR sample contained a mixture of comparable amounts of retinal isomers (BR-570 and 13- cis , 15- syn or BR-548)]. Excellent agreement was found between the vibrational features observed by PR/CARS and those obtained from spontaneous resonance Raman measurements from the same isotopically substituted BR pigments. Several new vibrational features were also found from the PR/CARS data. Vibrational Raman data from three of the isotopic BR samples in D₂O are reported for the first time.     

The ν1 and ν3 Bands of the OOO Isotopomer of Ozone

Using 0.002 cm⁻¹ resolution Fourier transform absorption spectra of an ¹⁷O-enriched ozone sample, an extensive analysis of the ν₃ band together with a partial identification of the ν₁ band of the ¹⁷O¹⁶O¹⁷O isotopomer of ozone has been performed for the first time. As for other C_2v-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3–16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers ν₀(ν₃) = 1030.0946 cm⁻¹ and ν₀(ν₁) = 1086.7490 cm⁻¹ were obtained for the ν₃ and ν₁ bands, respectively.     

Fourier transform infrared spectrum of the ν3 band of HCO

The ν₃ fundamental band of the formyl radical, HCO, in the 5.3-μm region has been observed at high resolution (0.0025 cm⁻¹, unapodized) using a Fourier transform spectrometer. The HCO radicals were formed by the reaction of F atoms with H₂CO in a fast-flow multiple-traversal absorption cell. A total of 298 lines were measured with an accuracy of about 0.0004 cm⁻¹ and assigned to transitions with values of the rotational quantum numbers N and K_a up to 20 and 5, respectively. These data greatly improve the knowledge of the HCO ν₃ line positions and (v₁v₂v₃) = (001) vibrational state molecular parameters as compared to earlier laser magnetic resonance studies of this band, especially for higher values of N. The ν₁ fundamental band of HCO was also observed and an analysis of these data agrees well with the recent study of Dane et al. [J. Chem. Phys. 88, 2121–2128 (1988)].     

Magnetic and electric hyperfine interactions in the system EuSm

Magnetic and electric hyperfine interactions in the system EuSm were investigated with the isomeric 11/2^– state in¹⁴⁵Eu by applying the time-differential perturbed angular distribution (TDPAD) method. The temperature dependence of paramagnetism was studied between 90 K and 1000 K by measuring the magnetic hyperfine interaction frequency _L=g_NN¹ (T)B_ext. The paramagnetic correction factor strictly follows the Curie-Weiss relation =1+C/(T-), withC=–50(2) K and =–29(5) K. This is compatible with a hyperfine field ofB _int(0)=–25(1) T, a valence of two for Eu in Sm, and antiferromagnetic order at low temperatures.The temperature dependence of the electric quandrupole coupling constant v_Q, investigated between 100 K and 400 K, can be reproduced by a linear temperature variation v_Q(T)=v_Q(0) (1-AT), with v_Q(0)=16.2(4) MHz andA=7.2(8)·10^–4 K^–1.The paramagnetic relaxation time _rel of the nuclear alignment is proportional to the temperature of the sample, with _rel T^–1=3.7(2) ·10^–9s K^–1.This leads to the Korringa relation _J T=const=5.1(5)·10^–11s K for the relaxation time of the 4f electronic spinJ. Assuming that the relaxation ofJ is mainly caused by exchange interaction between conduction electrons and localized 4f electrons at the Eu site, an exchange integral of |J _eff|=0.10(2) eV can be deduced.     

High-Resolution Study of the BaI AΠ Electronic State

Near-infrared and visible spectra of the A²Π–X²Σ⁺, C²Π_1/2–A²Π_1/2, C²Π_1/2–B²Σ⁺, and C²Π_1/2–X²Σ⁺ band systems of the BaI molecule were recorded by using Fourier transform spectroscopy (FTS). The spectra were produced from the chemiluminescent reaction Ba + I₂ and also by using laser-induced fluorescence (LIF) technique in which the laser sources were a Ti:sapphire single-mode laser, a dye single-mode laser, and a Kr⁺ multimode ion laser. Resolved rotational data, originating from 19 vibrational levels (0 ≤ v ≤ 5 and 7 ≤ v ≤ 19) of the A²Π state, 24 vibrational levels (0 ≤ v ≤ 18 and 20 ≤ v ≤ 24) of the X²Σ⁺ state, and 8 vibrational levels (1 ≤ v ≤ 2 and 9 ≤ v ≤ 14) of the C²Π state, were used in the final analysis. Previously recorded data for the B²Σ⁺–X²Σ⁺ and C²Π–X²Σ⁺ systems, taken from R. F. Gutterres, J. Vergès, and C. Amiot, J. Mol. Spectrosc. 196, 29–44 (1999) and from C. A. Leach, A. A. Tsekouras, and R. N. Zare, J. Mol. Spectrosc. 153, 59–72 (1992), were added to the present work data field. Accurate and improved molecular constants, for the X²Σ⁺, B²Σ⁺, A²Π, and C²Π states, were derived from a simultaneous treatment of the whole data set.     

The oxidation of fullerene [C70] with various oxidants by ultrasonication

The reaction of C₇₀ by ultrasonication with various oxidants such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and oxone^® monopersulfate compound, at room temperature causes the oxidation of fullerene [C₇₀(O)_n] (n=1–2 or n=1). The FAB-MS, UV–visible, FT-IR spectra, and HPLC analysis confirmed that products of fullerene oxidation are [C₇₀(O)_n] (n=1–2 or n=1).     

Fourier spectrometry: Rovibrational analysis of an infrared Π → Σ system of yttrium monoiodide

The infrared spectrum of yttrium monoiodide has been excited in an electrodeless microwave discharge and explored between 2500 and 12 000cm⁻¹ with a high-resolution Fourier transform spectrometer. A unique system is observed (ν₀₀ = 9905.520 cm⁻¹), which we attribute to a ¹Π → ¹Σ transition and an extensive analysis is made. Rovibrational constants are obtained for both states mainly from a simultaneous multiband fitting. This procedure is applied to the whole set of 2231 observed line wavenumbers in the 1-0, 0-0, and 0–1 bands, yielding a final weighted standard deviation of 0.0038 cm⁻¹. Furthermore, a partial analysis of the 2-0 and 3-1 bands is performed. The following equilibrium constants are derived (cm⁻¹): ω′_e=192.210 ω′_ex′_e=0.463B′_e=0.0399133 α′_e=0.0001150ω″_e=215.815 ω″_ex″_e=0.514B″_e=0.0422163 α″_e=0.0001125 High-order constants D_v and H_v are also calculated for the various vibrational levels (v′ = 0, 1, 2, 3; v″ = 0, 1).     

The microwave spectrum of 1-phosphabut-3-ene-1-yne, CH2=CHCP

The new molecule 1-phosphabut-3-ene-1-yne, CH₂=CHCP, produced by pyrolyzing prop-1-ene-3-phosphorus dichloride, CH₂=CHCH₂PCl₂, was detected by microwave spectroscopy. The analysis of the rotational transitions indicates that the molecule is planar with constants: A₀ = 46 694(24), B₀ = 2807.7100(21), and C₀ = 2645.8356(21) MHz. These rotational constants indicate that the structure of the vinyl group is essentially the same as that in CH₂=CHCN and CH₂=CHCCH; r(C---C) = 1.432 Å and (C=C---C) = 123.9°. The dipole moment parameters are μ_A = 1.181(2), μ_B = 0.074(1), and μ = 1.183(2) D. The vibrational satellite spectra for the C---CP bending modes indicate that ν₁₁(a′) = 184 ± 30 cm⁻¹ and ν₁₅(a″) = 263 ± 30 cm⁻¹.     

High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of NF3

The 2ν₃ overtone (A₁, E) and the ν₁ + ν₃ (E) combination bands of the oblate symmetric top ¹⁴NF₃ were studied by FTIR spectroscopy with a resolution of 2.5 × 10⁻³ cm⁻¹. Nearly 500 lines up to K_max/J_max = 30/43 were observed for the weak A₁ component reaching the v₃ = 2⁰ substate (1803.1302 cm⁻¹), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v₃ = 2^±2 substate (1810.4239 cm⁻¹), about 3550 transitions were assigned up to K_max/J_max = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v₃ = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v₃ = 2⁺² side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10⁻³  cm⁻¹. As for the ν₁ + ν₃ (E) combination band, about 3690 lines were assigned up to K_max/J_max = 45/55. Its v₁ = v₃ = 1 upper state (1931.577 5 cm⁻¹) was treated using the same model recently applied to the v₃ = 1 (E, 907.5413 cm⁻¹) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10⁻³  cm⁻¹ in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v₃ = 2 state, the D-, L-, and LD-reductions led to similar σ’s, while the Q one was not successful. For the v₁ = v₃ = 1 state, the D- and Q-reductions gave comparable σ’s, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v₃ = 2 state than for the v₁ = v₃ = 1 state. The three derivable anharmonicity constants in cm⁻¹ are x₃₃ = −4.1528, g₃₃ = +1.8235 and x₁₃ = −7.9652.     

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).     

Vector-spinor space and field equations

Generalizing the work of Einstein and Mayer, it is assumed that at each point of space-time there exists a vector-spinor space with N_v vector dimensions and N_s spinor dimensions, where N_v=2k and N_s=2 ^k, k3. This space is decomposed into a tangent space with4 vector and4 spinor dimensions and an internal space with N_v–4 vector and N_s–4 spinor dimension. A variational principle leads to field equations for geometric quantities which can be identified with physical fields such as the electromagnetic field, Yang-Mills gauge fields, and wave functions of bosons and fermions.     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

Polarization spectroscopy of ion-pair states of ICl

Molecular constants for the E0⁺(³P₂) and 1(³P₂) ion-pair states of ICl vapor have been determined using sequential two-photon polarization-labeling spectroscopy. The two states are coupled by a heterogeneous perturbation which is analyzed in some detail for low-lying vibrational levels of 1(³P₂). The I³⁵Cl potential constants for the 1(³P₂) state and the rotation-vibration constants for the set of f sublevels—i.e., the constants unaffected by coupling with the E state—are (in cm⁻¹) 1(³P₂): Y_0,0= 39103.814(32), Y_1,0= 170.213(15), Y_2,0= −0.4528(22), Y_3,0= −7.0(12) × 10⁻⁴, Y_4,0= −1.48(24) × 10⁻⁵ and Y_5,0= −6.6(19) × 10⁻⁸, Y^(f)_0,1= 5.6878(17) × 10⁻² Y^(f)_1,1= −2.110(24) × 10⁻⁴, Y^(f)_2,1= −1.23(62) × 10⁻⁷, and Y^(f)_0,1= −3.08(22) × 10⁻⁸Likewise, the I³⁵Cl constants determined for the E 0⁺(³P₂) state are E 0⁺(³P₂: Y_0,0= 39054.38(61), Y_1,0= 166.96(10), Y_2,0 = −0.3995(42), Y_0,1= 5.738(31) × 10⁻², and Y_1,1= −1.67(26) × 10⁻⁴Practical constraints in pumping the sequence E 0⁺ ← B 0⁺ ← × 0⁺ restrict the analysis of the E state to levels v = 9–15. Given the long extrapolation to the equilibrium state the 3σ statistical uncertainties quoted for these constants should be treated with caution.