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1.
Laser-induced fluorescence excitation has been used to measure Stark splittings of selected lines in the A?1A2-X?1A1 and a?3A2-X?1A2 band systems of H2CS in electric fields up to 13 kV/cm. The derived excited state a-axis dipole moments are 0.820 ± 0.007 D for the 41 level of the 1A2 state; 0.838 ± 0.008 D for the zeroth vibrational level of 1A2; and 0.534 ± 0.015 D for the zeroth vibrational level of the 3A2 state. These results are compared with the corresponding values of H2CO, and interpreted in terms of the changing localization of the π and π1 orbitals accompanying electronic excitation.  相似文献   

2.
The fundamental bands of the CF radical in the X2Π12 and X2Π32 electronic states were observed by using an infrared tunable diode laser as a source. Zeeman modulation could be used in detecting lines not only in the 2Π32 state, but also in 2Π12, because the CF radical deviates considerably from Hund's case (a). From the least-squares analysis of the observed spectra, the following molecular constants were obtained: Be = 1.416 704 (37) cm?1, αe = 0.018 419 (50) cm?1, re = 1.271 977 (17) A?, De = 6.68 (15) × 10?6cm?1, p0 = 0.008 580 (21) cm?1, p1 = 0.008 52 (11) cm?1, and ν0 = 1286.1281 (5) cm?1, with three standard errors in parentheses.  相似文献   

3.
We present a new technique for selectively populating excited states which are inaccessible by dipole excitation from the ground state. The method uses a static electric field to introduce a component of a dipole-allowed state into the state of interest. We have applied the method to cesium to measure lifetimes and a Stark mixing coefficient. The results are τ(62D52)=64(2) ns, τ(72D52)=92.5(15) ns, and <62D52|;ez |72P32>/(E7P?E6D)=0.7(3)×10?3 where is in kV/cm. 141  相似文献   

4.
The v = 1 ← 0 vibration-rotation bands of the NS radical in the X2Π12 and X2Π32 electronic states were observed by using a tunable diode laser. From the least-squares analysis the band origins were determined to be 1204.2755(12) and 1204.0892(19) cm?1, respectively, for X2Π12 and X2Π32. The rotational and centrifugal distortion constants and the internuclear distance in the X2Π electronic state were obtained as follows: Be = 0.775549(10) cm?1, De = 0.00000129(33) cm?1, and re = 1.49403(4) A?, with three standard deviations indicated in parentheses.  相似文献   

5.
Medium resolution infrared grating spectra of gaseous ketene, H2CCO were recorded between 1000 and 400 cm?1, both at instrument temperature (40°C) and with cooling (?40°C). Interferometric Fourier spectra were also measured at ?70°C with resolution 0.22 cm?1 between 450 and 330 cm?1. The K structure of the fundamentals ν5, ν6, ν8, and ν9 was assigned. These fundamentals are coupled by a-axis Coriolis interactions. These couplings were analysed on the symmetric top basis for setting up the perturbation matrix and by utilizing the K-dependent Coriolis shifts of levels. A preliminary analysis of the Coriolis intensity anomalies was also undertaken.Band center values from combination differences are ν50 = 587.30 (27) and ν60 = 528.36 (39) cm?1. Synthetic spectra indicate the band origins of ν8 and ν9 to be close to 977.8 and 439.0 cm?1, respectively. Estimates of Coriolis coupling constants obtained from synthetic spectra are ζ58a = + 0.33 (5), ζ68a = + 0.714 (20), ζ59a = ? 0.774 (20), and ζ69a = ? 0.30 (2). Approximate ratios of unperturbed vibrational transition moments obtained from spectral simulations are M80:±iM50:±iM60:M90 ≈ +2:?9:+10:+0.5.  相似文献   

6.
Predissociations in the y1Πg and x1Σg? Rydberg states of N2 (configurations u?14pσ and u?13pπ, respectively) and their likely causes, are discussed. Peaking of rotational intensity at unusually low J values, without sharp breaking off, is interpreted as due to case c? or case ci predissociation. Λ doubling in the y state, attributed to interactions with the x1Σg? state and with another, 1Σ+, state of the same electron configuration as x, is analyzed. From this analysis the location of the (unobserved) 1Σg+ state, here labeled x′, is obtained. It is concluded that the predissociation in the Π+ levels of the y state is an indirect one mediated by the interaction with x′ coupled with predissociation of x′ by a 3Σg? state dissociating to 4S + 2P atoms: combined, however, with perturbation of the y state by the k1Πg Rydberg state (configuration g?14dπ), whose Π+ levels are completely predissociated.  相似文献   

7.
A weak emission spectrum of I2 near 2770 Å is reanalyzed and found to to minate on the A(1u3Π) state. The assigned bands span v″ levels 5–19 and v′ levels 0–8. The new assignment is corroborated by isotope shifts, band profile simulations, and Franck-Condon calculations. The excited state is an ion-pair state, probably the 1g state which tends toward I?(1S) + I+(3P1). In combination with other results for the A state, the analysis yields the following spectroscopic constants: Te = 10 907 cm?1, De = 1640 cm?1, ωe = 95 cm?1, R″e = 3.06 A?; Te = 47 559.1 cm?1, ωe = 106.60 cm?1, R′e = 3.53 A?.  相似文献   

8.
The rotational motion of the OH? ion was studied in cubic NaOH at 575 K with quasielastic incoherent neutron scattering. The data are compared to two simple models yielding values for the radius of rotation R, the translational mean square displacement 〈u2H, the rotational jump rate τ?1 and the rotational diffusion coefficient DR. The following parameter values are obtained: (a) rotational jump model: R = 0.95 A?, 〈u2H = 0.052 A?2, τ?1 = 2 meV, (b) rotational diffusion model: R = 0.99 A?, 〈u2H = 0.046 A?2, DR = 0.72 meV.  相似文献   

9.
An electric field spectrum of thioformaldehyde has been measured for the 401 vibronic band of the A?1A2-X?1A1 electronic transition, using a tunable dye laser as the radiation source. Measurements of the Stark splittings of a number of lines in electric fields up to 8.7 kV/cm lead to a value of 0.79 ± 0.04 D for the excited state dipole moment. The decrease of dipole moment on excitation is compared with the equivalent change in formaldehyde and with predictions from ab initio calculations.  相似文献   

10.
The results of a vibrational and rotational analysis of the banded a?3A2X?1A1 transition in CH2SCD2S are presented. Only three of the six vibrational modes are active in the spectrum with ν′2 = 13201012, ν′3 = 859798, and 2ν′4 = 711516cm?1. The spin forbidden transition gains intensity primarily by a mixing of the 1A11,π) and 3A21,n) states. This is confirmed by a rotational analysis of the 000 band of both isotopes. The rotational analysis shows that the coupling in the a?3A2 state is near Hund's case b and that the spin constants are nearly 10 times greater than those observed for CH2O. A CNDO2 calculation shows that this difference is due to the greater spin orbit coupling of S in CH2S and to the smaller energy differences between the B?1A11,π), b?3A11,π), X?1A1, and the a?3A21,n) states. The r0 structure calculated from the rotational constants is rCS = 1.683 A?, rCH = 1.082 A?, βHCH = 119.6°, and α (out of plane) = 16.0°. A simultaneous fit of the vibrational levels in ν4 of CH2S and CD2S to a double minimum potential function yielded a barrier to molecular inversion of 13 cm?1 and an equilibrium out-of-plane angle of 15°.  相似文献   

11.
Relative oscillator strengths in the Cameron system of CO(a3Π ← X1Σ) have been observed in absorption for six bands (υ′ = 0–5, υ″ = 0) with the result, normalized to the absolute (0, 0) band measurement of Hasson and Nicholls, ?00 = (1.62±0.07) × 10?7, ?10 = (1.96±0.09) × 10?7, ?20 = (1.41±0.04) × 10?7, ?3 0 = (0.72±0.03) × 10?7, ?40 = (0.31±0.02) × 10?7, ?50 = (0.14±0.01) × 10?7. The density of CO was modulated with a motor-driven vacuum valve and synchronous fluctuations (?1 per cent) in the transmitted intensity detected with a lock-in amplifier. Peak pressure in the 21 cm absorption cell was approximately 10 torr. A curve of growth analysis was used to correct saturation effects by less than 3 per cent.  相似文献   

12.
The 6? and 7? isomeric states in 66Ga and 68Ga at 1440.9 and 1229.6 keV, respectively, have been populated with the (13C, 2np) and (15N, n2p) reactions on natural Fe. The half-lives of these states have been measured to be T12(6?, 66Ga) = 57.3 ± 1.2 ns and T12(7?, 68Ga) = 64 ± 2 ns. Using previous data on the hyperfine field of Ga in Fe, the g-factors of these states have been determined by means of the TDPAD method. The results are g(6?, 66Ga) = 0.129 ± 0.003 and g(7?, 68Ga) = 0.105 ± 0.003. These values are in very good agreement with the independent particle model if one assumes the f52, νg92}6?,7? and p32, νg92}6? configurations and uses the empirical proton and neutron g-factors from odd-A neighboring nuclei instead of the Schmidt values. The large disagreements with experiment when Schmidt values are used show that core polarization effects are important in these nuclei.  相似文献   

13.
The Raman active fundamentals ν1(A1g), ν2(Eg), ν5(F2g), and the overtone 2ν6 of SF6 have been investigated with a higher resolution and the band origins were estimated to be: ν1 = 774.53 cm?1, ν2 = 643.35 cm?1, ν5 = 523.5 cm?1, and 2ν6 = 693.8 cm?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν6 fundamental frequency is calculated as 347.0 cm?1. From the analysis of the ν2 Raman band, the following rotational constants of both the ground and upper states have been calculated:
B0 = 0.09111 ± 0.00005cm?1; D0 = (0.16±0.08)10?7cm?1
;
B2 = 0.09116 ± 0.00005cm?1; D2 = (0.18±0.04)10?7cm?1
.  相似文献   

14.
Using the re-equilibration kinetic method the chemical diffusion coefficient in nonstoichiometric chromium sesquisulfide, Cr2+yS3, has been determined as a function of temperature (1073–1373 K) and sulphur vapour pressure (10?104 Pa). It has been found that this coefficient is independent of sulphur pressure and can be described by the following empirical equation: D?Cr2+yS3=50.86 exp(-39070 cal/mole/RT) (cm2s?1). It has been shown that the mobility of the point defects inCr2+yS3 is independent of their concentration and that the self-diffusion coefficient of chromium in this sulfide has the following function of temperature and sulphur pressure: DCr=2.706×102P?14.85S2exp(-56070 cal/mole/RT). (cm2s?1).  相似文献   

15.
The B?X? band system of NO2, 2Σ?gu) ← 2A1, has been measured in absorption in a neon matrix at 6 K, using 15NO2 and N18O2 in addition to the normal isotope. The spectrum consists essentially of a single, long progression of bands terminating on successive levels of the bending mode in the upper state. Transitions to odd- and even-v2′ states occur with a uniform intensity distribution indicating that the rotation of the bent ground state of NO2 about its near-prolate axis is hindered in the matrix. The observations strongly suggest that the top axis of the molecule coincides with a C2 axis of neon crystals in the polycrystalline matrix. Relative to the vapor absorption the matrix spectrum is red shifted by about 150 cm?1, the crystal field parameter V2 and principal constants of the B? state of 14N16O2 in neon being
T010 14 571 cm?1: x22, ?0.3 cm?1;
w2 460.2 cm?1: V2, 80 cm?1.
  相似文献   

16.
The E-B (0g+-0u+) band system of Br2 has been investigated at Doppler-limited resolution using polarization labeling spectroscopy. Merged E state data for the three naturally occurring isotopes in the range vE = 0–16, expressed in terms of the constants for 79Br2, are (in cm?1) Y0,0 = 49 777.962(54), Y1,0 = 150.834(22), Y2,0 = ?0.4182(28), Y3,0 = 6.6(11) × 10?4, Y0,1 = 4.1876(28) × 10?2, Y1,1 = ?1.607(16) × 10?4, and Y0,2 = 1.39(39) × 10?8. The bond distance is re = 3.194 A?, and the diabatic dissociation energy to Br+(3P2) + Br?(1S0) is 34 700 cm?1.  相似文献   

17.
The Coriolis interactions between ν1 and ν3, and between ν2 and ν3 in SO2 have been analyzed to obtain the signs of the products ζ3.1c(a?Q3)(b?Q1) and ζ3.2c(a?Q3)(b?Q2). It has been found that both of the signs of these products are positive. Then, relative signs of (?Q1) have been determined using the calculated values of the Coriolis zeta constants for the present definition of the normal coordinates. The obtained sign combination of (?Qi) is ±(+?+), which agrees with the one predicted by the molecular orbital calculations. Using the sign combination (+?+), the polar tensors of S and O atoms were also calculated.  相似文献   

18.
The non-selective nature of the (α, nγ) reaction has been used to complement information from charged-particle reactions on the level structure of 88Y and 90Y. The γ-ray spectra were recorded with a 25 cm3 Ge(Li) detector at 90° to the beam using primarily targets of 85Rb2CO3 and 87Rb2CO3 and α-particle energies of 11.8, 12.2 and 13.0 MeV. The resulting transitions were accommodated in level schemes that involved primarily the following shell model configurations: p12)1g92)?1, g92)?1g92)1, p12)1p12)?1, f52)?1g92)?1 in 88Y and p12)1d52)1, πg(92)1d52)1,p12)1s12))1 in 90Y.  相似文献   

19.
The nuclear quadrupole hyperfine splittings of Pr3+ in LaF3 have been measured for the ground electronic state using a RF optical resonance technique. A hamiltonian H = P[(I2z? 13I(I+1) + (η/6)(I2+?I2-)] was fitted to the data with zP=4.185 ± 0.003 MHzandη = 0.105 ± 0.010. Linewidths of 180 kHz were observed.  相似文献   

20.
Magnetoelastic excitations with a fine structure in the 50kHz range have been observed in the study of the domain wall resonance (DWR) in magnetic garnet thin films. DWR excites standing transverse elastic waves which have a resonance frequency given by f=nv2d, where f is the frequency, n is an integer, v=3.5×105 cm/sec is the transversal velocity of the elastic wave, and d=0.05 cm is thickness of the film/substrate system. A fine structure associated with each of these modes has been identified as due to two dimensional bulk elastic waves by using a set of parallel microstrip lines. The dispersion relation of these elastic waves is ω2=v2(k21+k22), where ω is the radial frequency, k1 and k2 are the wave vectors in the orientation perpendicular and parallel to the sample surface respectively. In the case of k1?k2, f=f0+v2k22f0, where f0 is the resonance when k2=0. The experimental results are in excellent agreement with this model. A linear dispersion, observed when using a shorted slot-line structure, is understood as the excitation of three dimensional modes due to the complex structure of the slot-line and the sample geometry.  相似文献   

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