Observed and calculated interactions between valence states of the NO molecule

No perturbation between two valence states of NO has ever been identified, although many valence-Rydberg and several Rydberg-Rydberg perturbations have been extensively studied. The first valence-valence crossing to be experimentally documented for NO is reported here and occurs between the ¹⁵N¹⁸O B²Π (v = 18) and B′²Δ (v = 1) levels. No level shifts larger than the detection limit of 0.1 cm^?1 are observed at the crossings near $\text{J = 6.5 [B}{}^2\text{Π}\text{(F}{}_1\text{) ～ B′}{}^2\text{Δ}\text{(F}{}_2\text{)]}$ and $\text{J = 12.5 [B}{}^2\text{Π}\text{(F}{}_1\text{) ～ B′}{}^2\text{Δ}\text{(F}{}_1\text{)]}$; two crossings involving higher rotational levels could not be examined. Semi-empirical calculations of spin-orbit and Coriolis perturbation matrix elements indicate that although the electronic part of the $\text{B}{}^2\text{Π}\text{～ B′}{}^2\text{Δ}$ interaction is large, a small vibrational factor renders the ¹⁵N¹⁸O B (v = 18) ? B′ (v = 1) perturbation unobservable. Semi-empirical estimates are given for all perturbation matrix elements of the operators $\text{Σ}{}_{\mathrm{i}}\text{a}\text{?}{}_{\mathrm{i}}\text{l}{}_{\mathrm{i}}\text{·s}{}_{\mathrm{i}}$ and $\text{B(L}{}_{\mathrm{\pm }}\text{S}{}_{\mathrm{?}}\text{? J}{}_{\mathrm{\pm }}\text{L}{}_{\mathrm{?}}\text{)}$ which connect states belonging to the configurations $\text{(σ2p)}{}^2\text{(π2p)}{}^4\text{(π}{}^1\text{2p)}$, $\text{(σ2p)(π2p)}{}^4\text{(π}{}^1\text{2p)}{}^2$, and $\text{(σ2p)}{}^2\text{(π2p)}{}^3\text{(π}{}^1\text{2p)}{}^2$.     

Theoretical analysis of the centrifugal distortion contributions to the rotational spectra of 2Π diatomics

The centrifugal distortion contributions to the rotational energies of diatomic molecules are derived from the resolution of the vibration-rotation wave equation. The unknown radial dependence of the fine structure constants is taken into account by means of a Taylor expansion around the equilibrium distance. Hence, one obtains the expressions of the centrifugal corrections associated with each fine structure constant in terms of the equilibrium values of its radial derivatives. The case of ²Π states is examined in detail. The dependence of the centrifugal distortion effects upon the choice of the coupling scheme representation is exhibited and a ²Π energy matrix containing the centrifugal constants of any order is proposed. Such a matrix is appropriate to fit the data for any value of the rotational quantum number. The theoretical expressions of the energy levels are related to the experimental data and the correlations between the spin-orbit centrifugal and spin-rotation contributions are put in evidence. It is shown that very compact formulas can be derived allowing a straightforward evaluation of the successive radial derivatives of the spin-orbit function in terms of the spectroscopic data $\text{A}{}^{\mathrm{(1)}}\text{? ?α}{}_{\mathrm{A}}\text{(}\text{w}{}_{\mathrm{e}}\text{B}{}_{\mathrm{e}}\text{)}$; $\text{A}{}^{\mathrm{(2)}}\text{? ?(1 +}\text{α}{}_{\mathrm{B}}\text{w}{}_{\mathrm{e}}\text{2B}{}_{\mathrm{e}}{}^2\text{)A}{}^{\mathrm{(1)}}$; …. Application of these results to the case of several molecules is considered and discussed.     

Observation of interference between Iu=12 and Iu=32 baryon exchange amplitudes in 4 GeV/c backward inelastic scattering

Interference between the $\text{I}{}_{\mathrm{<mtext>u</mtext>}}\text{=}\text{1}\text{2}$ and $\text{I}{}_{\mathrm{<mtext>u</mtext>}}\text{=}\text{3}\text{2}$ baryon exchange amplitudes is observed in the reaction π^?p → pπ^?π⁰, with the proton produced forward with $\text{cos}\text{θ}{}_{\mathrm{p}}{}^1\text{>0.8}$. The Dalitz plot shows that the reaction is dominated by the quasi two body final states ρ^?p(δ exchange) and $\text{N}{}^{10}\text{(1670)π}{}^0\text{(}\text{N exchange}\text{)}$, with δ(1238), N¹(1520) and higher mass N¹'s also produced. The relative phase between the ρ and the N¹(1670) production amplitudes is measured to be 135° ± 10° and is compared with the Regge pole signature factor phase predictions.     

The ã3A2 ← X̃1A1 absorption spectrum of thioformaldehyde: A vibrational and rotational analysis

The results of a vibrational and rotational analysis of the banded $\text{a}\text{?}{}^3\text{A}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1$ transition in $\text{CH}{}_2\text{S}\text{CD}{}_2\text{S}$ are presented. Only three of the six vibrational modes are active in the spectrum with $\text{ν′}{}_2\text{=}\text{1320}\text{1012}$, $\text{ν′}{}_3\text{=}\text{859}\text{798}$, and $\text{2ν′}{}_4\text{=}\text{711}\text{516}\text{cm}{}^{\mathrm{?1}}$. The spin forbidden transition gains intensity primarily by a mixing of the ${}^1\text{A}{}_1\text{(π}{}^1\text{,π)}$ and ${}^3\text{A}{}_2\text{(π}{}^1\text{,n)}$ states. This is confirmed by a rotational analysis of the 0₀⁰ band of both isotopes. The rotational analysis shows that the coupling in the $\text{a}\text{?}{}^3\text{A}{}_2$ state is near Hund's case b and that the spin constants are nearly 10 times greater than those observed for CH₂O. A $\text{CNDO}\text{2}$ 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 $\text{B}\text{?}{}^1\text{A}{}_1\text{(π}{}^1\text{,π)}$, $\text{b}\text{?}{}^3\text{A}{}_1\text{(π}{}^1\text{,π)}$, $\text{X}\text{?}{}^1\text{A}{}_1$, and the $\text{a}\text{?}{}^3\text{A}{}_2\text{(π}{}^1\text{,n)}$ states. The r₀ structure calculated from the rotational constants is $\text{r}{}_{\mathrm{<mtext>CS</mtext>}}\text{= 1.683}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>CH</mtext>}}\text{= 1.082}\text{A}\text{?}$, β_HCH = 119.6°, and α (out of plane) = 16.0°. A simultaneous fit of the vibrational levels in ν′₄ 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°.     

Hyperfine structure of CH3OH

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 $\text{C}{}_{\mathrm{JK\tau \pm }}{}^{\mathrm{(i)}}$ and $\text{D}{}_{\mathrm{JK\tau \pm }}{}^{\mathrm{(i)}}$, respectively, are in kHz¹: $\text{C}{}_{101}{}^{\mathrm{(1)}}\text{= 2.4(10)}$, $\text{C}{}_{101}{}^{\mathrm{(2)}}\text{= ?0.6(10)}$, $\text{D}{}_{101}{}^{\mathrm{(1)}}\text{= ?13.8(9)}$, $\text{D}{}_{101}{}^{\mathrm{(2)}}\text{= 7.0(9)}$, $\text{C}{}_{\mathrm{213?}}{}^{\mathrm{(1)}}\text{= ?5.0(10)}$, $\text{C}{}_{\mathrm{213?}}{}^{\mathrm{(2)}}\text{= ?5.5(10)}$ and ($\text{C}{}_{\mathrm{J13?}}{}^{\mathrm{(2)}}\text{- C}{}_{\mathrm{J13+}}{}^{\mathrm{(2)}}\text{) = 0.98(9)}$.     

Microwave spectrum of the IO radical

The two lowest rotational transitions of the IO radical in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ ground electronic state have been observed by means of a Stark modulated spectrometer. The effective rotational constants in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state, the centrifugal distortion constant, the axial component of the magnetic hyperfine interaction, and the nuclear electric quadrupole coupling constant are determined accurately. It was necessary to take into account the second-order effects from the matrix elements off-diagonal in J for the analysis of the hyperfine structure. An equilibrium internuclear distance r_e is calculated to be 1.8677 ± 0.0028 Å from the effective rotational constant $\text{B}{}_0\text{(}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{)}$, combined with α₃ from the A²Π → X²Π transition.     

Neutron-proton shell model multiplets in 88Y and 90Y from a study of the (α, nγ) reaction

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: $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$, $\text{(π}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^1$, $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$, $\text{(π}\text{f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$ in ⁸⁸Y and $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^1$, $\text{π}\text{g}\text{(}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^1$,$\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2)</mtext>}}\text{)}{}^1$ in ⁹⁰Y.     

The fluorescence excitation spectrum of s-tetrazine cooled in a supersonic free jet

The fluorescence excitation spectrum of the ${}^1\text{B}{}_{\mathrm{3u}}\text{(v′ = 0) ←}{}^1\text{A}{}_{\mathrm{g}}\text{(v″ = 0)}$ transition in s-tetrazine has been observed and measured. The sample was cooled to a rotational temperature of <1 K by expansion in a supersonic free jet. In this way the rotational structure arising from asymmetry split low J lines could be observed. The rotational A and B axes of the ²H₁¹²C₂¹⁴N₄ isotope were observed to interchange upon electronic excitation and a theory describing the effect of this interchange upon the optical selection rules has been developed. Analysis of the resolved rotational structure suggests that the geometry change upon electronic excitation is smaller than that deduced from previous analysis of the room temperature optical spectrum.     

Reorientational motion of the OH− ion in cubic sodium hydroxide

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 〈u²〉_H, the rotational jump rate τ^?1 and the rotational diffusion coefficient D_R. The following parameter values are obtained: (a) rotational jump model: $\text{R = 0.95}\text{A}\text{?}$, $\text{〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.052}\text{A}\text{?}{}^2\text{, τ}{}^{\mathrm{?1}}\text{= 2}\text{meV}$, (b) rotational diffusion model: $\text{R = 0.99}\text{A}\text{?}\text{, 〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.046}\text{A}\text{?}{}^2\text{, D}{}_{\mathrm{R}}\text{= 0.72}\text{meV}$.     

A multipole analysis of pion photoproduction in the first resonance region

An energy-independent multipole analysis of pion photoproduction in the first resonance region has been performed in which special care has been taken in the selection and normalization of the data. The results obtained are a significant improvement on those of earlier analyses. Three features are of particular interest: a zero in the $\text{E}{}_{\mathrm{1+}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ multipole at resonance; a smooth $\text{M}{}_{\mathrm{1?}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ multipole showing the onset of the P₁₁(1470) resonance; and evidence for the position of the Δ⁺ resonance being different from those of the Δ⁺⁺ and Δ^o resonances. A comparison is made with the recent energy-dependent analyses, indicating agreement in the gross features of the multipoles but showing significant differences in essential details.     

Stark effect in the torsio-rotational spectrum of propargyl mercaptan and SH bond moment determination

The Stark effect of rotational and torsio-rotational transitions of propargyl mercaptan has been analyzed. Assuming a dependence of the dipole moment components on the internal rotation angle of the type: $\text{μ}{}_{\mathrm{a}}\text{= μ}{}_{\mathrm{a}}{}^0\text{+ μ}{}_{\mathrm{a}}{}^{\mathrm{(1)}}\text{cos}\text{α}$, $\text{μ}{}_{\mathrm{b}}\text{= μ}{}_{\mathrm{b}}{}^0\text{+ μ}{}_{\mathrm{b}}{}^{\mathrm{(1)}}\text{cos}\text{α}$, and $\text{μ}{}_{\mathrm{c}}\text{= μ}{}_{\mathrm{c}}{}^{\mathrm{(1)}}\text{sin}\text{α}$, the following values of the determinable quantities were obtained: $\text{μ}{}_{\mathrm{a}}{}^{\mathrm{<mtext>eff</mtext>}}\text{= 0.718 ± 0.003}\text{D}$, $\text{μ}{}_{\mathrm{b}}{}^{\mathrm{<mtext>eff</mtext>}}\text{= 0.495 ± 0.010}\text{D}$, and $\text{μ}{}_{\mathrm{c}}{}^{\mathrm{(1)}}\text{= 0.809 ± 0.015}\text{D}$.The SH bond moment was also evaluated from $\text{μ}{}_{\mathrm{c}}{}^{\mathrm{(1)}}$ and compared with the SH bond moment of similar molecules.     

Study of the 12C(12C,n)23Mg reaction around the resonance at Ecm = 19.3 MeV

A strong selectivity of the ¹²C(¹²C,n)²³Mg reaction is observed in a resonance at $\text{E}{}_{\mathrm{<mtext>cm</mtext>}}\text{(}{}^{12}\text{C) = 19.3}\text{MeV}$. The neutron spectra and n-γ coincidence measurements show evidence for population of high-spin members of the ground- state rotational band in ²³Mg.     

The ultraviolet absorption spectrum of thioformaldehyde

The spectra of H₂CS and D₂CS were surveyed over the wavelength region from 230 to 180 nm and four distinct absorptions were identified. These are assigned to transitions from the $\text{X}\text{?}{}^1\text{A}{}_1$ ground state to the $\text{B}\text{?}{}^1\text{A}{}_1\text{(π, π}{}^1\text{)}$, $\text{C}\text{?}{}^1\text{B}{}_2\text{(n, 3s)}$, $\text{D}\text{?}{}^1\text{A}{}_1\text{(n, 3p}{}_{\mathrm{y}}\text{)}$, and $\text{E}\text{?}{}^1\text{B}{}_2\text{(n, 3p}{}_{\mathrm{z}}\text{)}$ electronic states. A vibrational and rotational analysis of the second system was undertaken. The results indicate that the molecule is planar in the $\text{C}\text{?}{}^1\text{B}{}_2\text{(n, 3s)}$ state and that while the CH and CS bond lengths remain near their ground-state values, the HCH angle increases substantially.     

High-resolution tunable spectroscopy of rotational transitions of NO near 30 cm−1

The rotational spectrum of ¹⁴N¹⁶O is studied in the far infrared. The monochromatic tunable far-infrared radiation is generated by mixing the radiatin of an HCN laser with that of a tunable klystron. Five rotational transitions in both the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ states are observed in the frequency region between 852 and 1053 GHz. The results are compared with the known RF, microwave, and IR data.     

Methyl barrier to internal rotation and quadrupole coupling constants in S-methylchlorothioformate

Internal rotation A-E splittings have been observed in the ground state for both ³⁵Cl and ³⁷Cl isotopic species of S-methylchlorothioformate. The values $\text{V}{}_3\text{(}{}^{35}\text{Cl}\text{) = 893 ± 20}$ and $\text{V}{}_3\text{(}{}^{37}\text{Cl) = 890 ± 20 cal/mole}$ have been obtained. The anaalysis of the hyperfine structure gave $\text{χ}{}_{\mathrm{aa}}\text{(}{}^{35}\text{Cl}\text{) = ?49.2}$, $\text{χ}{}_{\mathrm{bb}}\text{(}{}^{35}\text{Cl}\text{) = 22.4}$ and $\text{χ}{}_{\mathrm{aa}}\text{(}{}^{37}\text{Cl}\text{) = ?39.0}$, $\text{χ}{}_{\mathrm{bb}}\text{(}{}^{37}\text{Cl) = 18.3 MHz}$. Only the syn-conformation of the methyl group with respect to the carbonyl group has been observed. A partial r₀ structure is given.     

Backbending behaviour of rotational bands in 163,165,167Yb

Several rotational bands in ^163,165,167Yb are observed in (HI,xnγe^?) experiments. The $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ and $\text{3}\text{2}{}^{\mathrm{?}}\text{[521]}$ bands do not backbend, whereas the $\text{5}\text{2}{}^{\mathrm{?}}\text{[523]}$ bands do, indicating additional processes besides the rotational alignment of one $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ neutron pair that are responsible for the backbending.     

Microwave optical double resonance and continuous wave dye laser excitation spectroscopy of NO2: Rotational assignment of the K = 0−4 subbands of the 593 nm band

A rotational assignment of approximately 80 lines with K_a′ = 0, 1, 2, 3, and 4 has been made of the 593 nm ${}^2\text{A}{}_1\text{→}{}^2\text{B}{}_2$ band of NO₂ using cw dye laser excitation and microwave optical double-resonance spectroscopy. Rotational constants for the ²B₂ state were obtained as A = 8.52 cm^?1, B = 0.458 cm^?1, and C = 0.388 cm^?1. Spin splittings for the K_a′ = 0 excited state levels fit a simple symmetric top formula and give $\text{(?}{}_{\mathrm{bb}}\text{+ ?}{}_{\mathrm{cc}}\text{)}\text{2}\text{= ?0.0483}\text{cm}{}^{\mathrm{?1}}$. Spin splittings for K_a′ = 1 (N′ even) are irregular and are shown to change sign between N′ = 6 and 8. Assuming that the large inertial defect of 4.66 amu Ų arises solely from A, a structure for the ²B₂ state is obtained which gives $\text{r}\text{(NO) = 1.35}\text{A}\text{?}$ and an ONO angle of 105°. Alternatively, weighting the three rotational constants equally gives $\text{r = 1.29}\text{A}\text{?}$ and θ = 118°.     

Laser magnetic resonance spectrum of BrO (2Π12 ← 2Π32)

Magnetic dipole transitions between the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ components of the ground electronic state of BrO have been detected using the technique of laser magnetic resonance on three CO₂ laser lines between 964 and 970 cm^?1. This is the first direct observation of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state in BrO. The spin-orbit splitting parameter, A, is determined to be ?967.9831(2) cm^?1 for ⁷⁹Br¹⁶O and ?967.9981(2) cm^?1 for ⁸¹Br¹⁶O. Accurate values for the rotational constant $\text{B}{}^{\mathrm{<mtext>eff</mtext>}}\text{(}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}$, the hyperfine parameters ($\text{b}{}_{\mathrm{F}}\text{+}\text{2c}\text{3}$) and d, the Λ-doubling parameter p, and the Zeeman parameter g| are also determined from an analysis of the measured spectra.