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1.
The pure rotational spectra of H212C17O and H213C17O have been investigated in the frequency region between 8 and 360 GHz in the ground vibrational state. For both isotopic species the 17O nuclear quadrupole coupling constants and spin-rotation constants have been obtained. From both Q- and R-branch transitions a set of rotational constants and several distortion constants could be derived employing Watson's formalism in A reduction. The obtained rotational constants are in Megahertz:
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2.
The ν2 (CO stretching) vibration-rotation bands of H2CO and D2CO near 5.8 μm have been studied using the technique of laser Stark spectroscopy. The following vibrational and rotational constants have been determined:
H212C17OH213C17O
A281 965.0 (30)281 987.3 (19)
B37 812.287(45)36 776.790(25)
C33 214.523(31)32 412.920(19)
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3.
The high dispersion absorption spectrum of the Ag2 molecule has been photographed in the ~5300–1500-Å region. Observations include the previously reported AX, BX, CX, DX, and EX transitions and a new HX transition which occurs in the vacuum ultraviolet. Extensive spectral blending precluded detailed rotational analyses, but the band structures are consistent with ΔΩ = 0 and ΔΩ≥1 for D-X and C-X, respectively. The H state is perturbed and probably predissociated. The following molecular constants (in cm?1) were obtained from fitting bandhead data to the usual expressions:
ConstantH2COD2COUnit
ν01746.0111701.620cm?1
A′281807.8 ± 6.141696.6 ± 7.MHz
B′38608.7 ± 5.32068.4 ± 7.MHz
C′33738.7 ± 3.25998.6 ± 10.MHz
μ″2.328 ± 0.0062.344 ± 0.006Debye
μ′2.344 ± 0.0062.364 ± 0.005Debye
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4.
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,
StateTeωcXωt
X0.0192.00.58
B35 838.6151.80.87
C37 631.6171.00.84
D39 014.5168.21.20
E40 159.9146.11.58
H58 273.1165.92.46
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5.
Combination of the results of two sets of measurements on the same crystalline samples of CsCdF3 and KZnF3 has made possible the evaluation of the third-order elastic (TOE) constants of these two fluoroperovskites. In the first technique the hydrostatic pressure dependence of the velocity of ultrasonic waves of different propagation and polarization directions has been measured to determine three linear combinations of TOE constants. In the second technique the fundamental and the second harmonic amplitudes of an initially sinusoidal longitudinal ultrasonic wave of finite amplitude propagating along the principal directions have been measured to determine three other linear combinations. Combination of the two sets of data leads to the following room temperature values of the TOE constants (in units of 1012 dynes/cm2):
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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6.
The ν4 and the ν9 bands of CF2CH2 have been studied using coincidences with the 10.4 μm band of the CO2 laser and the 10.9 μm band of the N2O laser. These resonances have been analyzed, together with recent microwave results, to give the following vibration-rotation parameters and dipole moments in the ν4 and ν9 states
SampleC111C112C114C166C123C456
CsCdF3?13·2?4·55?3·12?0·69+2·6?3·8
KZnF3?16·6?4·75?0·52?1·79+3·2?6·87
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7.
The ν3 fundamental band (CO stretch) of HDCO at 1724 cm?1 has been studied using both conventional infrared absorption and CO laser Stark spectroscopy. In addition to the excited-state (v3 = 1) rotational constants, improved constants for the ground state of HDCO have been obtained by combining previous microwave data with some infrared combination differences. The following constants were determined:
ν4 CF2CH2ν9 CF2CH2
ν0925.7692 (2)953.8057 (2)cm?1
A10 971.99 (2)11 026.918 (6)MHz
B10 414.98 (2)10 436.381 (6)MHz
C5328.48 (2)5346.100 (6)MHz
μ1.382 (1)1.382 (1)D
μ - μ00.014 (2)0.004 (1)D
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8.
The ν1 fundamental band of the ClO2 radical has been studied by means of the 10.6-μm CO2 and N2O laser Stark spectroscopy. More than 250 and 150 Stark resonances were assigned for the 35ClO2 and 37ClO2 species, respectively, and were analyzed together with the recent microwave and laser-microwave double resonance results to give molecular constants including spin-rotation interaction constants. The ν1 band origins and electric dipole moments both in the ground and ν1 states were determined accurately
ConstantGround statev3 = 1 stateUnits
ν01724.267cm?1
A198 119.75198 210.4MHz
B34 910.64634 676.6MHz
C29 561.48829 331.3MHz
μa2.33022.3486D
μb0.1950.190D
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9.
The rotational spectrum of the new reactive triatomic molecule chloro(sulphido)boron, ClBS, produced by the high-temperature reaction of gaseous dichloro disulphide, Cl2S2, and crystalline boron at ca. 1000°C was studied by microwave spectroscopy between 26.5 and 40 GHz. Ground state rotational constants have been obtained for 11 of the 12 isotopic variants involving 35Cl, 37Cl, 11B, 10B, 32S, 33S, and 34S; the isotopic shifts for the ground state lines of 35Cl10B34S from those of 35Cl11B34S are too small and they are overlapped by the 11B species. The abundance of rotational constant data has allowed a detailed comparison of various structure determination procedures to be made. The substitution method yields an extremely consistent ClS distance of 3.28715 ± 0.00005 Å. Application of the first moment condition allows the B atom, which lies close to the center of mass, to be quite accurately located. The resulting bond lengths are r(ClB) = 1.681 ± 0.001 A? and r(BS) = 1.606 ± 0.001 A?. The more important derived spectroscopic parameters are:
35ClO237ClO2
ν0945.592 357(60)939.602 909(66)cm?1
μ′1.788 39(13)1.788 46(15)D
μ″1.791 95(10)1.792 10(13)D
δμ?0.003 56(18)?0.003 64(26)D
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10.
The ν2 and ν3 fundamentals of FNO have been recorded with a Fourier transform spectrophotometer at an apodized resolution of approximately 0.004 cm?1. The Fourier infrared data have been analyzed together with previous microwave data to yield improved molecular parameters for the (000) and (010) vibrational states and the first set of constants for the (001) state. The main results (in cm?1) are
35Cl11B32S35Cl10B32S37Cl11B32S35Cl10B32S
B02796.7796(7)2796.8613(14)2722.9999(6)2723.2127(17) MHz
D0344.0(8.0)327.0(17.0)321.0(7.0)328.0(21.0) Hz
α2?7.4889(7)?7.8745(15)?7.2941(15)?7.6742(17) MHz
α33.4620(2)3.7731(4)3.4755(2)3.6354(3) MHz
q21.9942(9)1.9160(7)1.8954(7)1.8190(7) MHz
eQq(Cl)?42.54(1)?42.56(2)?33.53(1)?33.58(3) MHz
μ1.45(8)— D
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11.
The spectrum of OCS with natural isotopic abundances has been measured in the 1975- to 2140-cm?1 region with near-Doppler-limited resolution using a Fourier transform spectrometer. Sixteen bands have been analyzed, including the following five bands for the first time at high resolution:
Ground stateν2ν3
A3.1751882 (17)3.1861249 (12)3.1958722 (15)
B0.39508266 (12)0.39407878 (14)0.39211484 (14)
C0.35051504 (11)0.34899779 (16)0.34747411 (14)
ν00765.3551 (4)519.5980 (4)
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12.
The ν3 band of CD3F has been studied using coincidences with the 10.4 μm band of the CO2 laser. The majority of the 150 resonances measured have been studied using the Lamb dip technique. These resonances have been analyzed, together with recent microwave results, to give the following vibration-rotation parameters and dipole moments in the ν3 state.
16O13C32S1000-00002009.228 cm?1
16O13C32S1110-01102002.427 cm?1
18O12C32S1000-00002026.147 cm?1
16O12C32S0400-00002104.828 cm?1
16O12C32S0510-01102115.169 cm?1
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13.
The measurements of the microwave spectrum of BrF were carried out on the hyperfine components of J = 1 ← 0 and J = 2 ← 1 rotational transitions of 79BrF and 81BrF. A direct diagonalization procedure of the energy matrix of the total Hamiltonian including Stark effect has been used. The following constants were derived:
12CD3F
ν0992.29882 (19)cm?1
B20395.776 ± 0.08MHz
A-A0?35.73 ± 0.61MHz
DJ33.8 ± 0.5kHz
DJK203.9 ± 7kHz
μν31.8964 ± 0.0015D
μν3 ? μ00.02617 ± 0.0005D
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14.
Using CO2 and N2O lasers, we have measured and assigned nineteen ν4 and nine ν6 rotation-vibration resonances of the type ΔM = 0 and M = J. These transitions were combined with the zero-field pure rotational spectra in order to determine the two fundamental vibrational frequencies, the rotational constants of both excited states, the Coriolis coupling constant, and the dipole moments of each of the three states. The ground-state rotational constants and centrifugal distortion constants were taken from a microwave study and the centrifugal distortion constants of the excited states were assumed equal to those of the ground state. The following results were obtained (standard deviations in parentheses):
79BrF
81BrF
Be (MHz) 10 667.610 (60)
10 616.522 (70)
eq0Q (MHz) 1086.80 (30)
908.09 (20)
eq1Q (MHz) 1085.66 (60)
907.41
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15.
The ν2 (CD3 symmetrical deformation) and ν5 (CD3 degenerate deformation) fundamental bands of CD3Br were studied by 9.4- and 10.4-μm CO2 laser Stark spectroscopy. Stark resonances originating from 28 and 53 rovibrational transitions of the ν2 and ν5 bands, respectively, were assigned for each of the isotopic species, CD379Br and CD381Br. These two bands were simultaneously analyzed with explicit inclusion of the ν2-ν5 Coriolis interaction, yielding precise molecular constants in the ν2 and ν5 excited states as well as the Coriolis coupling constant. The molecular constants obtained are consistent between the two isotopic species and are in good agreement with the results of high-resolution infrared studies. The band origins and dipole moments are
ν4ν6
ν0938.0345 (6)989.2519 (18)(cm?1)
A139 579 (150)143 323 (150)(MHz)
B31 873.6 (5)32 379.5 (7)(MHz)
C26 242.9 (6)25 994.4 (8)(MHz)
ξ64(a)136 178 (770)(MHz)
μ2.319 (10)2.347 (4)(D)
μ(ground state)2.3464 (8)(D)
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16.
Stark-shifted microwave transitions in the ground and ν2 vibrational states of H2CO were observed by means of CO laser-microwave double-resonance with intense electric field. High sensitivity and precision were attained by the use of multireflection absorption cell, optical-flat Stark plates, and microwave frequency stabilization. Dipole moments determined from some individual rotational transitions in the ground and ν2 vibrational states are, in Debye, with uncertainties in parentheses,
CD379BrCD381Br
ν2991.396 82 (18)991.388 46 (17)cm?1
ν51055.469 00 (12)1055.466 32 (12)cm?1
μ01.830 42 (52)1.829 84 (47)D
μ21.829 93 (48)1.829 57 (46)D
μ51.832 23 (60)1.831 19 (56)D
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17.
The collision-induced fundamental infrared absorption band of hydrogen in binary mixtures H2He and H2Ne at 77, 195, 273, and 298 K has been studied with absorption path lengths of 27 and 105 cm for gas densities up to 530 amagat for several base densities of hydrogen. In each of these mixtures the enhancement absorption profiles show, in addition to the usual splitting of the Q branch into the main QP and QR components, a splitting of the S(1) line into the SP(1) and SR(1) components at all the experimental temperatures and a secondary splitting of the main QP component into the QP(3) and QR(3) components at 273 and 298 K. The profiles of H2He at 77 K also show a splitting of the S(0) line into SP(0) and SR(0). Integrated absorption coefficients were measured and binary and ternary absorption coefficients were derived. Van Kranendonk's theory of the ‘exponential-4’ model for the induced dipole moment was applied to the experimental binary absorption coefficients. The quadrupolar parts of these coefficients were calculated from the known molecular parameters and were then subtracted from the experimental values to obtain the overlap parts. The overlap parameters λ and ρ, giving respectively the magnitude and range of the overlap moment, were determined for each of the mixtures by obtaining the best fit of the calculated overlap part of the binary absorption coefficient as a function of temperature to the experimental values of the overlap parts. The values of λ, ρ, and μ(σ) (the overlap induced dipole moment at the Lennard-Jones intermolecular diameter σ) are as follows:
TransitionG.S.ν2δμ
110 ← 1112.3315 (1)2.3472 (1)0.0157 (1)
211 ← 2122.3313 (1)2.3471 (1)0.0158 (1)
312 ← 3132.3313 (1)2.3470 (1)0.0157 (1)
826 ← 8272.3311 (1)2.3466 (1)0.0155 (1)
927 ← 9282.3466 (1)
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18.
Doppler-limited laser excitation spectra for four bands of PrO have been recorded: System XvII 0-0, System XXI 0-0 and 0–1, and the 0-0 intercombination between the upper and lower states, respectively, of Systems XVII and XXI. First lines in R and P branches prove that Systems XVII and XXI are, respectively, Ω′ = 4.5 ? Ω″ = 3.5 and Ω′ = Ω″ = 4.5. Hyperfine components are well resolved for all four excitation bands. Rotational and hyperfine constants are determined by least-squares fits of data from all four bands together. In addition, fluorescence spectra, recorded from various J′, v′ = 0 levels of the upper states of Systems XVII and XXI, reveal five new low-lying states. Principal constants (in cm?1) for nine Ω-states follow (1σ uncertainty in parentheses):
Mixtureλρμ(σ)
H2He5.6 × 10?30.24 Å2.92 × 10?2ea0
H2Ne9.0 × 10?30.29 Å4.85 × 10?2ea0
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19.
About two hundred Stark resonances of the ν2 and ν5 vibration-rotation bands of CD335Cl, using a 9.4 μm CO2 laser as a source, have been measured. By combining these data with the zero-field microwave spectra the following molecular constants have been determined (with the standard deviations in parentheses):
StateTvBvd(hfs)
Ω′ = 4.5 (System XXI)18 882.388 (2)0.353001 (18)0.12403 (71)
Ω′ = 4.5 (System XVII)16 594.075 (1)0.353736 (20)0.12977 (67)
Ω″ = 3.53 887.15 (16)0.35751 (28)
Ω″ = 3.52 931.66 (15)0.35712 (21)
Ω″ = 4.52 155.16 (30)0.36264 (67)
Ω″ = 5.52 099.16 (31)0.35079 (71)
Ω″ = 3.52 064.34 (13)0.35654 (20)
Ω″ = 4.5 (System XXI)217.383 (1)0.362134 (20)0.27744 (66)
Ω″ = 3.5 (System XVII)0.00.360948 (16)?0.00809 (85)
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20.
BS2, trapped in neon matrices at 4°K, exhibits extensive progressions in the A2Πu ← X2Πg and B2Σu+ ← X2Πg systems. From these transitions, those observed in the infrared, and a reinterpretation of gas-phase data, the following molecular constants (in solid neon) are obtained for linear symmetric 11BS2 (in cm?1):
ν2ν5
ν01 028.67275 (15)1 059.96970 (11)(cm?1)
A78 765.20 (89)78 030.21 (109)(MHz)
B110 805.29 (26)10 860.10 (13)(MHz)
5?25 080.77 (99)(MHz)
D8 756.0 (43)(MHz)
μ1.90741 (33)1.90607 (36)(D)
μ(ground state)1.90597 (33)(D)
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B2Σu+T0 = 24,072ν1 = 516
A2ΠuT0 = 13.766ν1 = 506
A0 = ?263ν2 = 311
ν3 = 1535
X2ΠgA0 = ?440ν1 = 510
ν2 = ~120
ν3 = 1015
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