Microwave measurements and calculations of quadrupole coupling effects in CH3I and CD3I

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 $\text{eQq}{}_0\text{+ aJ(J + 1) + bK}{}^2\text{+}\text{cK}{}^4\text{J(J + 1)}$. 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.     

An X-Y Coriolis perturbation in ν4 of CD3Br

The region 2242–2273 cm^?1 of the ν₄ band in CD₃Br was remeasured at a resolution limit of 0.025 cm^?1. Line assignments were extended up to J = 50 in some subbands. Transitions in the KΔK = ?8 subband were assigned, and the perturbation apparent in this region was attributed to the x-y Coriolis interaction with ν₃ + ν₅^±1 + ν₆^±1. The x-y Coriolis coupling parameter W_xu and the ν₃ + ν₅^±1 + ν₆^±1 band center (in cm^?1) are 0.01960 and 2339.17 for CD₃⁷⁹Br, while the corresponding values for CD₃⁸¹Br are 0.01956 and 2337.95.     

Beam maser measurements of hyperfine structure in chloroacetylene-d

The J = 1-0 transitions in ³⁵ClCCD were measured using a beam maser spectrometer giving a molecular resonance linewidth of 3 kHz (FWHM). Analysis of the data yielded quadrupole coupling strengths eqQ(D) = 208.5 ± 1.5, eqQ(³⁵Cl)= 79 739.5 ± 1 kHz and the ³⁵Cl spinrotation interaction strength C(Cl) 1.3 ± 0.1 kHz. The rotational constant obtained is B = 5 186 973.9 ± 1.0 kHz. The accuracy of measured molecular parameters is improved by a factor of 20 or better.     

Investigation of the ν5 band of methylacetylene by infrared laser Stark and microwave spectroscopy

Microwave spectra have been studied in the ground and v₅ = 1 (CC stretching mode) states of methylacetylene. From these data, dipole moments and rotational and centrifugal distortion constants have been determined, as follows: μ_D⁽⁰⁾ = 0.7839 ± 0.0010 D, μ_D⁽⁵⁾ = 0.7954 ± 0.0010 D, B₅ = 8508.119 ± 0.003 MHz, D_J⁽⁵⁾ = 1.8 ± 0.2 kHz, and D_JK⁽⁵⁾ = 169 ± 1 kHz. Laser Stark spectra have been obtained for the ν₅ band of this molecule and from these spectra the following vibration-rotation parameters have been determined: ν₅⁰ = 93.27540 ± 0.00007 cm^?1, A₅ - A₀ = ?227.0 ± 2.3 MHz and D_K⁽⁵⁾ - D_K⁽⁰⁾ = ?0.05 ± 0.50 MHz. The higher-J and -K states of the v₅ = 1 state appear to be purturbed.     

Radiofrequency spectroscopy inside a laser cavity: Nuclear quadrupole resonance and A1-A2 splitting of CH3Br

The highly sensitive method of infrared-radiofrequency double resonance inside a CO₂N₂O laser cavity has been applied to the observation of “pure” nuclear quadrupole resonance and direct A₁-A₂ transitions of CH₃Br. More than 150 quadrupole resonances have been observed for ¹²CH₃⁷⁹Br, ¹²CH₃⁸¹Br, ¹³CH₃⁷⁹Br, and ¹³CH₃⁸¹Br using direct double resonance as well as collision-induced satellites. Accurate hyperfine constants, i.e., the quadrupole coupling constant eqQ and its rotational dependence χ_J and χ_K, Hougen's coefficient χ_d, and the spin-rotation constants C_N and C_K have been determined for the ground state. The eqQ in the excited states ν₃, ν₆, ν₃ + ν₆, and 2ν₆ have also been determined. About 60 direct l-doubling transitions have been observed, which has enabled us to determine the l-doubling constant q_v(1,1), its rotational dependence δq_v^J(1,1) and the asymmetry parameter for the quadrupole coupling constant eqQη for the ν₆ and ν₃ + ν₆ states. A set of direct A₁-A₂ transitions in the 2ν₆ state with K = 1 and l₆ = ?2 and that in the ν₆ state with K = 2 and l₆ = ?1 have been observed. The rovibrational and isotope assignments of the observed A₁-A₂ are helped by the existence of quadrupole hyperfine structure and many collision-induced satellites. The rovibrational assignments of CH₃Br transitions which are coincident with laser lines are summarized.     

Precise nuclear moments of extremely proton-rich nuclus 23 Al

Electric quadrupole coupling constant eqQ/h of the extremely proton-rich ²³Al (I ^π ?=?5/2^?+?, T _1/2?=?0.47 s) nucleus implanted into an Al₂O₃ single crystal has been measured for the first time, using the β-ray detecting nuclear quadrupole resonance method (β-NQR) in a high magnetic field. As a preliminary result, the quadrupole coupling constant was determined as |eqQ/h(²³Al) |?=?2.66±0.77 MHz. Using the quadrupole coupling constant of ²⁷Al in Al₂O₃ as a reference, the Q moment of the ground state of ²³Al was extracted as |Q(²³Al)|?~?160 mb, which is well explained by the shell model calculation in the sd-shell model space with the USD interaction.     

Millimeter-wave spectrum of the C4v molecule IOF5: l-type doubling of the kl = −1 transitions in the v11(E) = 1 state spectrum

Measurements of the rotational spectrum of the C_4v molecule IOF₅ are reported for the excited vibrational state v₁₁(E) = 1 for the transitions J13 ← 12, 14 ← 13, 16 ← 15, and 17 ← 16 (55–72 GHz) including the observation of the kl = −1 (q⁻), l-doubling effect. Detailed assignments of the E-state spectrum are presented based on the overlapping quadrupole structure. These data are analyzed together with earlier results for the excited vibrational state v₆(B₁) = 1 to give information concerning the ν₆(B₁)-ν₁₁(E) Coriolis interaction and the (Δl, Δk) = (2, 2) (q⁺) and (2, −2) (q⁻)l-resonance interactions. It is found that q₁₁⁻ = −2.57(10) MHz, |q₁₁⁺| = 0.094(20) MHz, Δ = ν₆ − ν₁₁ = 45.2(7) cm⁻, ζ_11,11^z = +0.18(1) and |ζ_6,11^y| = 0.73(4).     

Determination of A0 from the ν4 Raman band of CD3Br

The principles and methods of determining A₀ from the Raman spectra of degenerate fundamentals of C_3v molecules are outlined, and applied to the ν₄ band of CD₃Br to yield a value of A₀ = 2.6004 ± 0.0010 cm^?1.     

Microwave spectrum,conformation, quadrupole coupling constants,and barrier to internal rotation of methoxyamine

The microwave spectra of three isotopic species of methoxyamine (CH₃ONH₂) have been studied. For the normal species the ground-state rotational constants are A = 42488 ± 150 MHz, B = 10049.59 ± 0.03 MHz, and C = 8962.85 ± 0.03 MHz. From these data and those from the -NHD and -ND₂ species, the amino protons have been shown to occupy a symmetrical trans position relative to the methyl group. The barrier to internal rotation of the methyl group has been found to be 873 ± 15 cm^?1 by analysis of ground-state splittings. Analysis of hyperfine splittings has yielded the ¹⁴N quadrupole coupling constants, which have the following values for the normal isotopic species: χ_aa = 3.63 ± 0.03 MHz, χ_bb = ?3.69 ± 0.07 MHz, and χ_cc = 0.06 ± 0.07 MHz.     

The microwave spectrum of 1-phosphapropyne,CH3CP: Molecular structure,dipole moment,and vibration-rotation analysis

The J = 4 ← 3 and J = 3 ← 2 rotational transitions of 1-phosphapropyne, CH₃CP, between 26.5 and 40 GHz have been studied by microwave spectroscopy. The spectrum shows the characteristic vibration-rotation satellite patterns associated with a C_3v symmetric rotor. Apart from the most abundant isotope variant, the species ¹²CD₃¹²C³¹P, ¹²CD₂H¹²C³¹P, ¹²CH₂D¹²C³¹P, ¹³CH₃¹²C³¹P, ¹²CH₃¹³C³¹P, ¹³CD₃¹²C³¹P, and ¹²CD₃¹³C³¹P have also been studied. For ¹²CH₃¹²C³¹P the rotational constants B₀ = 4991.339 ± 0.003 MHz, D_J = 0.823 ± 0.092 kHz, D_JK = 66.59 ± 0.18 kHz have been determined. From these data the following structural parameters have been derived: $\text{r}{}_{\mathrm{s}}\text{(}\text{CH}\text{) = 1.107 ± 0.001}\text{A}\text{?}$, ∠_s(HCC) = 110.30 ± 0.09°, $\text{r}{}_{\mathrm{s}}\text{(}\text{CC}\text{) = 1.465 ± 0.003}\text{A}\text{?}$, $\text{r}{}_0\text{(}\text{CP}\text{) = 1.544 ± 0.004}\text{A}\text{?}$. The dipole moment has been determined as 1.499 ± 0.001 D by analysis of the Stark effect of the J = 3 ← 2, |K| = 1 line. The vibrational satellites (v_s = 1, 2, and 3) have been studied and various vibration-rotation parameters derived.     

High resolution infrared spectrum of the ν4 band of DCCF

The bending vibration-rotation band ν₄ of DCCF was studied. The measurements were carried out with a Fourier spectrometer at a resolution of about 0.03 cm^?1. The constants B₀=0.29141(1)cm^?1, α₄=?5.02(2)×10^?4cm^?1, q₄=4.52(3)×10^?4cm^?1, and D₀=9.2(4)×10^?8cm^?1 were derived. The rotational analysis of the “hot” bands 2ν₄(Δ) ← ν₄(II) and 2ν₄(Σ⁺) ← ν₄(II) was performed. In addition, the “hot” bands ν₄ + ν₅ ← ν₅ were assigned. A set of vibrational constants involved was derived.     

Rotational spectrum of sulfuryl bromide fluoride

The rotational spectra of SO₂⁷⁹BrF and SO₂⁸¹BrF have been obtained between 18 and 40 GHz. Both molecules are near-prolate symmetric rotors with a and b-type dipole components. A least-squares fit of the observed moments of inertia obtained by correcting for the bromine quadrupole interaction yields $\text{r}\text{(SBr) = 2.155 ± 0.006}\text{A}\text{?}$ and ? FSBr=100.6°±1.5° structural parameters when $\text{r}\text{(SO) = 1.407}\text{A}\text{?}$, $\text{r}\text{(SF) = 1.56}\text{A}\text{?}$, and ? OSO=123.7° are assumed.     

The Coriolis interaction between the fundamentals ν2 and ν5 of CD3Br

The bands ν₂ and ν₅ of CD₃Br have been measured at a resolution of 0.010 cm^?1. They were analyzed simultaneously by taking into account the xy-Coriolis interaction. More than 1600 transitions were assigned for each isotopic species CD₃⁷⁹Br and CD₃⁸¹Br. The Coriolis coupling term proved to be ζ_2,5^y = 0.559. The band centers are (in cm^?1) ν₂: 991.401 (CD₃⁷⁹Br), 991.390 (CD₃⁸¹Br); ν₅: 1055.474 (CD₃⁷⁹Br), 1055.471 (CD₃⁸¹Br).     

Theoretical integrated intensities for the 2ν2 and 2ν2-ν2 bands of HCN and DCN

Dipole moment functions, both perpendicular and parallel to the molecular axis, are calculated from the SCF and MRD-CI results of a previous study for the normal ν₂ bending vibrations of HCN and DCN. Vibrationally averaged dipole moments and the infrared transition matrix elements are then obtained from the dipole moment functions and vibrational wave functions. MRD-CI results, with known experimental values in parentheses, for HCN are 〈0|μ|0〉 = ?2.954(?2.985) D, 〈1|μ|1〉 = ?2.915(±2.942) D, 〈0|μ|1〉 = 0.148(0.147) D, 〈0|μ|2〉 = ?0.027 D, 〈1|μ|2〉 = 0.210 D. Calculated absolute intensities at 1 atm and 0°C for the (02⁰0) ← (000), (02⁰0) ← (010), and (02²0) ← (010) bands of HCN are 25 (40 ± 10 as estimated from spectra), 8.5, and 17.0 atm^?1 cm^?2, respectively. Results for DCN are also reported.     

The bending vibration bands ν4 and ν5 of HCCI

The bending vibration bands ν₄ and ν₅ of HCCI were studied. From the observed rotational structure the rotational constant B₀ and the centrifugal distortion constant D₀ were obtained. The results were B₀ = 0.105968(7) cm^?1 and D₀ = 1.96(7) × 10^?8 cm^?1 from ν₄ and B₀ = 0.105948(8) cm^?1 and D₀ = 1.96(11) × 10^?8 cm^?1 from ν₅. The structure of the hot bands 2ν₅(Δ) ← ν₅(Π) and 3ν₅(φ) ← 2ν₅(Δ) was also resolved and hence the values α₅ = ?3.033(8) × 10^?4 cm^?1 and q₅ = 9.3(3) × 10^?5 cm^?1 could be derived. The other most intense hot bands following ν₅ could be explained in terms of the Fermi diads $\text{ν}{}_3\text{2ν}{}_5{}^0$ and $\text{ν}{}_3\text{+}\text{ν}{}_5{}^{\mathrm{\pm 1}}\text{3ν}{}_5{}^{\mathrm{\pm 1}}$. Of the numerous hot bands accompanying ν₄, only those between different excited states of ν₄ could be assigned. Then estimates for α₄ and q₄ were also obtained. In addition, several vibrational constants were derived.     

The microwave spectrum of 4-pyridine carbaldehyde (isonicotinealdehyde)

The microwave spectrum of 4-pyridine carbaldehyde has been investigated in the region 8 to 40 GHz. Rotational transitions have been observed and assigned for the ground state and two excited states of the torsion mode. Analysis yields precise rotational constants (A = 5519.04 ± 0.08, B = 1559.17 ± 0.03, C = 1216.11 ± 0.02 MHz) which prove the molecule to be planar. Centrifugal distortion constants have also been obtained. Analysis of the observed ¹⁴N quadrupole fine structure yields the following quadrupole coupling constants (in MHz): χ_aa = ?4.67 ± 0.09; χ_bb = 1.19 ± 0.26; χ_cc = 3.48 ± 0.26. The electric field gradient about the nitrogen nucleus is thus similar to that of pyridine.     

Laser Stark and laser-microwave double-resonance spectroscopy of the ν2 band of CD3I

The ν₂ fundamental band of CD₃I was investigated by means of the laser Stark spectroscopy using a 10.6 μm CO₂ laser and an N₂O laser as infrared radiation sources. The assignment was established for about 150 Stakr resonances. Laser-microwave double resonance was used to confirm the assignment. A least-squares analysis of the Stark spectrum gave the molecular constants: μ″ = 1.6504 ± 0.0004 D; μ′ = 1.6479 ± 0.0005 D; ν₀ = 28 461 093.8 ± 3.6 MHz; A′ - A″ = 234.0 ± 1.1 MHz; D_K′ - D_K″ = 0.121 ± 0.085 MHz. The uncertainties are 2.5 times the standard deviations. The single and the double primes refer to the ν₂ and the ground vibrational states, respectively.     

Intense mass-separated beams of halogens and beta-delayed neutron emission from heavy bromine isotopes

Improved production yields of short-lived halogens were obtained from a ThO₂ target, irradiated with 600 MeV protons, in combination with a negative surface ionization source. Mass-separated samples were studied by decay spectroscopy. Production yields of radioactive isotopes of chlorine, bromine, iodine and astatine are presented. Half-lives and relative neutron emission probabilities were measured for the heavy bromine isotopes^89?92Br. Normalizing to earlier publishedP _n values for⁸⁹Br, the results are:⁸⁹Br (4.30±0.14s,P _n =13.6±0.8%),⁹⁰Br (1.92±0.06s,P _n =24.8±1.5%),⁹¹Br (0.53 ±0.03 s,P _n =30.1 ±2.1%), and⁹²Br (0.31 ±0.02 s,P _n =34.6±2.5%). Energy spectra ofβ-delayed neutrons were measured.     

Second-order Coriolis resonance between ν2 and ν5 of CH3F by microwave spectroscopy

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; $\text{B}{}_5{}^1$, 25 611.60 ± 0.40; A_ζ5, ?38 772 ± 116; $\text{B}{}_2{}^1$, 25 432.52 ± 0.33; D, 21 838.4 ± 8.2; $\text{q}{}_5{}^1$, 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; A_ζ6ηJ, ?0.562 ± 0.030; |q₆|, 8.70 ± 0.13 MHz. Errors are 2.5 times the standard deviations.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.