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1.
Resonance photoelectron spectra of methyl iodide have been taken by exciting individual autoionizing Rydberg states, and measuring the ejected electron energies by a time of flight technique. A number of spectra were obtained from autoionization states which are members of two series, converging respectively to the 2E12 (ν = 0) and 2E122 =1) states of the ion. In addition to observing vibrational bands not previously reported, we found that the peak intensities are consistent with Bardsley's formulation of the configuration interaction theory of autoionization.  相似文献   

2.
The transitions J = 1 ← 0, K = 0; J = 2 ← 1, K = 0; and J = 2 ← 1, K = 1 of CH3I and CD3I were measured using a Stark-modulated microwave spectrometer. Iodine quadrupole coupling strengths were analyzed to determine variations with deuterium substitution on the methyl group and variations with centrifugal distortion. Quadrupole coupling strengths were described by the expression eQq0 + aJ(J + 1) + bK2 + cK4J(J + 1). Explicit expressions are given for a, b, and c for a symmetric top in terms of molecular parameters. For CH3I eQq0 = ?1934.11 ± 0.02 MHz and for CD3I eQq0 = ?1928.95 ± 0.04 MHz. Rotational constants obtained are B(CH3I) = 7501.274 ± 0.002 MHz and B(CD3I) = 6040.298 ± 0.007 MHz. The observed fractional change in halogen quadrupole coupling of 0.0027 is related to previous results for methyl chloride and methyl bromide.  相似文献   

3.
Measurements of the absolute vibrational Raman intensities and depolarization ratios for the fundamental and some overtone and combination bands of CH4, CH3D, CH2D2, CHD3, and CD4 are reported. Experimental aspects of these measurements are discussed. The experimental data conform satisfactorily to all isotope intensity sum rules. The measured intensities and depolarization ratios, together with the vibrational potential function for CH4, make possible the calculation of the four independent parameters of the isotopic invariant quantities αS = |?S|. The results deduced from these agree with all 36 experimentally observed values. Values of electro-optical parameters for the CH bond are calculated and discussed.  相似文献   

4.
The multiplet splitting patterns of microwave transitions in the ground state and the first two torsional excited states of CH3OCH3, CD3OCD3, and CD3OCH3 were analyzed in terms of the semirigid rotor models C2vF-C3vT-C3vT and C3F-C3vT-C3vT?. The following nonzero potential coefficients were obtained for CH3OCH3: V30 = V03 = 909.05 ± 0.49 cm?1, V33 = 5.06 ± 1.60 cm?1; for CD3OCH3: V30(CD3) = 897.18 ± 2.41 cm?1, V03(CH3) = 910.45 ± 0.33 cm?1; for CD3OCD3: V30 = V03 = 897.00 cm?1. These results are compared to earlier microwave studies of these molecules.  相似文献   

5.
The J = 1 ← 0 and J = 2 ← 1 transitions and the l-doubling transitions of J = 2 – 6 of 12CH3F in the ν2 and ν5 states were analyzed by taking into account the Coriolis interaction between the two modes. The molecular constants which are derived are: ν5 - ν2, 252 412 ± 112; B51, 25 611.60 ± 0.40; Aζ5, ?38 772 ± 116; B21, 25 432.52 ± 0.33; D, 21 838.4 ± 8.2; q51, 39.58 ± 0.30 MHz; in addition to a few other minor constants. The present result is completely consistent with the recent Raman data of Escribano, Mills, and Brodersen, J. Mol. Spectrosc.61, 249 (1976). Molecular constants in the ν3 and ν6 states have also been obtained: B3, 25 197.570 ± 0.020; B6, 25 418.917 ± 0.047; Aζ6ηJ, ?0.562 ± 0.030; |q6|, 8.70 ± 0.13 MHz. Errors are 2.5 times the standard deviations.  相似文献   

6.
Rotational energy levels in vibronic ground states of 2A, 2E, and 2F electronic states of open-shell XY4 molecules, as well as rotational line intensities for allowed transitions between such states, are discussed, including the effects of spin-orbit interaction and tetrahedral splittings. Jahn-Teller effects are assumed to be small, and are only taken into account implicitly, through their contributions to various parameters in the effective Hamiltonian. Qualitative information is obtained by considering several limiting-case coupling schemes among the electron spin angular momentum S, the electron orbital angular momentum L, and the pure rotational angular momentum R. These limiting cases are similar in spirit to Hund's coupling cases in diatomic molecules, but differ sufficiently from the latter to make detailed correspondences unhelpful. Quantitative information on rotational energy levels and line intensities is obtained numerically by diagonalizing a Hamiltonian matrix set up in a basis set characterized by uncoupled moleculefixed projections of S, L, and the total angular momentum J, and symmetrized so that all basis set functions belong to a definite species in the subgroup D2d of the true point group Td. Hamiltonian matrix elements are determined by ladder operator techniques. Three sample calculated spectra, corresponding to p(2F2)-s(2A1), d(2E)-p(2F2), and d(2F2)-p(2F2) are presented. As one might expect, when the spin-orbit constant A is set equal to zero, then both qualitative and quantitative aspects of the rotational-electronic problem in open-shell XY4 molecules can be mapped easily onto discussions of the rotation-vibration problem from the CH4 literature.  相似文献   

7.
Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C2H3F, C2H3Cl, C2H3Br, C2H5F, C2H3CN, CH2CF2, HCOOH and CH3Br with a CO2 laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.  相似文献   

8.
The microwave spectrum of MnO3F has been remeasured and several corrections and new results have been obtained: B0 = 4129.141 MHz, DJ = 1.12 kHz, DJK = 1.87 kHz; α3B = 8.622, α5B = ? 11.994, α6B = 6.042, |q5| = 16.005, and |q6| = 8.456 MHz.  相似文献   

9.
10.
Second order elastic constants of NH4Cl and NH4Br crystals were measured under hydrostatic and uniaxial pressures near the λ-type phase transitions. Third order elastic constants were calculated from the pressure derivatives of the second order elastic constants. Results show that the temperature dependences of the third order elastic constants of NH4Cl differ from those of NH4Br dramatically. In addition, it is found that the coefficients 154(C111 + 6C112 + 2C123) and (124√3)(C111 ? 3C112 + 2C123) of strains in the free energy of NH4Cl show quite different temperature dependences from those of NH4Br.  相似文献   

11.
Measurements of the dielectric constants revealed a ferro- to paraelectric transition in methylammonium trichloromercurate (CH3NH3HgCl3). Thermal analysis by differential scanning calorimetry indicates a transition temperature of Tc ≈ 60°C. The structures of both phases were determined from single crystal X-ray measurements. The ferroelectric phase crystallizes at room temperature in the polar trigonal space group P32(a = b = 7.8117(3), c = 9.826(3)A?, Z = 3). The refinement of the ferroelectric structure included the fractional contribution of the two domains present. The paraelectric phase has monoclinic symmetry (space group C2 with a = 13.816(2), b = 7.880(1), c = 9.734(3)A?, β = 90.49(5)°, Z = 6) and contains an almost completely disordered methylammonium group while order with pronounced thermal motion is observed in the ferroelectric phase.  相似文献   

12.
Laser Stark spectroscopy of the ν3 band of CH3F has been carried out using coincidences with the 9.4 μm band CO2 laser lines. About 350 Stark resonances were measured for the ν3 fundamental bands of 12CH3F and 13CH3F. About 30 of them were measured by using a Stark-Lamb dip technique to increase the resolution and the accuracy of the data. These Stark resonances, together with the recent results of infrared-microwave two-photon Lamb dip measurements, were analyzed to give the following vibration-rotation parameters and the dipole moments in the ν3 state,
  相似文献   

13.
The ferro-paraelectric transition in Sr0.5Ba0.5Nb2O6 ceramics has been studied by measuring the dielectric pennitivity as a function of temperature at different frequencies. Experimental results in the transition region over ?'max fit the relation 1?' ?1?'max = A(T ? T0)γ with γ > 1, as is typical for dif transitions. In an interval of temperatures of 17°C over T0 (=Tfor?'max), γ = 2. Using the relaxors' model of Kirillov-Isupov an equation is inferred in order to compute the activation energy of the relaxors as a function of parameters directly obtained from the experimental results.  相似文献   

14.
We obtained twelve new far infrared laser transitions by optically pumping the CH2DOH, CH3I, CD3I and Trioxymethylene molecules with a CW CO2 laser having a tunability range of 280 MHz. We measured the wavelength, polarization, relative intensity and pump offset relative to the CO2 center frequency for all the new lines.  相似文献   

15.
Multi-kolowatt pulses with limited wavelength tunability have been produced in several bands between 186 and 817 m by pumping v3 P-branch transitions in12CH3F and12CD3F with the 10.6 m band of a ten-atmosphere CO2 laser. The FIR emissions are all restricted to the immediate neighborhood of the resonances associated with successive J-numbers, but there is some evidence that additional off-resonant emission could be produced with stronger pumping. The optimum operating pressure for the various molecule/J-number combinations range from 7 to 75 torr and increase rapidly with increasing J-number.  相似文献   

16.
Hyperfine structure of the (0, 0, 1) - (1, 0, 1) transition of methanol has been investigated by beam absorption and of the (J, 1, 3?) → (J, 1, 3+) transitions for J = 2, 3, and 6 by beam-maser spectroscopy. The best-fit results for the spin-rotation and spin-spin coupling constants CJKτ±(i) and DJKτ±(i), respectively, are in kHz1: C101(1) = 2.4(10), C101(2) = ?0.6(10), D101(1) = ?13.8(9), D101(2) = 7.0(9), C213?(1) = ?5.0(10), C213?(2) = ?5.5(10) and (CJ13?(2) - CJ13+(2)) = 0.98(9).  相似文献   

17.
The rotational spectrum of isothiocyanic acid was measured for the isotopically enriched species H15NCS and HN13CS as well as HNC34S in natural abundance. In the frequency range from 8 to 240 GHz the a-type R-branch transitions were measured for all three isotopic species. The qQ1 transitions were identified in the microwave region for H15NCS and HN13CS. The rotational and centrifugal distortion constants were determined using Watson's Hamiltonian in the S reduction, extended empirically to higher order terms in the angular momentum. The molecular structure of isothiocyanic acid was reevaluated using a modified substitution method and the NCS chain was found to be bent: r(NH) = 0.993 A?, r(NC) = 1.207 A?, r(CS) = 1.5665 A?, ∠HNC = 131.7°, and ∠NCS = 173.8°. The molecule has the trans conformation.  相似文献   

18.
The ν4 infrared and Raman bands of CH3Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH335Cl, including A0 = 5.20530 ± 0.00010 cm?1 and DK = (8.85 ± 0.13) × 10?5cm?1. For CH337Cl an incomplete set of constants was obtained from the infrared band, and A0 = 5.2182 ± 0.0010 cm?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is r(CH) = 1.0854 ± 0.0005 A?, r(CCl) = 1.7760 ± 0.0003 A?, and <(HCH) = 110°.35 ± 0°.05.  相似文献   

19.
The properties of polariton Raman spectra for the internal vibration region of NH4Cl crystal are discussed. These spectra have been recorded by means of a copper laser ( λ = 5105 and 5782A?) for sample temperature T=80 and 10°K.According to the theory a polariton singularities in the region of a polar bound state has been obtained. The two-particle bands have been studied and a very complicate structure inside of these bands has been revealed. Moreover, multiphonon singularities at polariton curves have been observed. The experimental polariton law has been compared to the theory and a conclusion has been made as to the necessity of a further development of the theory.  相似文献   

20.
Nuclear spectroscopic quadrupole moments of the radioactive isotopes 131Cs, 132Cs, and 136Cs have been determined from the hyperfine structure of the 62P32 state by the level crossing method. The results including a Sternheimer correction are: Qs(131Cs) = ?0.625(6) b, Qs(132Cs) = +0.508(7) b, Qs(136Cs) = +0.225(10) b. The quadrupole moments of all the Cs isotopes from A = 131 to A = 137 are recalculated. It is shown, that nuclear quadrupole moments of a specific isotope obtained from different atomic P-states only agree within the limits of error after application of the Sternheimer correction. The increase of Qs with decreasing neutron number conforms with other observations and theoretical calculations stating that for elements around Z = 55 nuclear deformation develops below N = 82. The staggering of the sign of Qs may be interpreted as consequence of an oblate-prolate degeneracy of the nuclear energy surface. Some magnetic moments have been slightly improved: μI(132Cs) = 2.219(7) μN, μI(136Cs) = 3.705(15)μN (corrected for diamagnetism).  相似文献   

12CH3F13CH3F
ν01048.610767 (62)1027.493191 (69)cm?1
B25197.57 ± 0.0324542.07 ± 0.43MHz
A - A0?294.09 ± 0.60?288.81 ± 0.37MHz
DJ55.5 ± 1.256 ± 12kHz
DJK575 ± 63464 ± 24kHz
μ1.9054 ± 0.00061.9039 ± 0.0006D
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