Polarization spectroscopy of the E0g+-B0u+ band system of Br2

The E-B (0_g⁺-0_u⁺) 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 v_E = 0–16, expressed in terms of the constants for ⁷⁹Br₂, are (in cm^?1) Y_0,0 = 49 777.962(54), Y_1,0 = 150.834(22), Y_2,0 = ?0.4182(28), Y_3,0 = 6.6(11) × 10^?4, Y_0,1 = 4.1876(28) × 10^?2, Y_1,1 = ?1.607(16) × 10^?4, and Y_0,2 = 1.39(39) × 10^?8. The bond distance is $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.194}\text{A}\text{?}$, and the diabatic dissociation energy to $\text{Br}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_2\text{) +}\text{Br}{}^{\mathrm{?}}\text{(}{}^1\text{S}{}_0\text{)}\text{is 34 700 cm}{}^{\mathrm{?1}}$.     

Analysis of the 2770-Å emission system in I2

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 $\text{I}{}^{\mathrm{?}}\text{(}{}^1\text{S) +}\text{I}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_1\text{)}$. In combination with other results for the A state, the analysis yields the following spectroscopic constants: T″_e = 10 907 cm^?1, $\text{D}$″_e = 1640 cm^?1, ω″_e = 95 cm^?1, $\text{R″}{}_{\mathrm{e}}\text{= 3.06}\text{A}\text{?}$; T′_e = 47 559.1 cm^?1, ω′_e = 106.60 cm^?1, $\text{R′}{}_{\mathrm{e}}\text{= 3.53}\text{A}\text{?}$.     

Rotational analysis of a vibronic band of gaseous CeF

Rotational analysis of an absorption band at 5679.4 Å leads to the following estimates of constants for the lower state, which is probably the ground state: B₀ = 0.240182(90) cm^?, ω = 589(13) cm^?1, and $\text{r}{}_0\text{= 2.0484(4)}\text{A}\text{?}$, where the values in parentheses are of 2σ.     

“Forbidden” rotational spectra of symmetric-top molecules: PH3 and PD3

A millimeter-wave spectrometer having a sensitivity of 4 × 10^?10 cm^?1 in the 2-mm region has been constructed for observation of extremely weak millimeter-wave spectra of gases. It has been used to measure J → J, K = 0 ← 3 transitions in PH₃ and J → J, K = 0 ← 3 as well as K = ±1 ← ±4 transitions in PD₃. The B₀ and C₀ spectral constants (in MHz) are: for PH₃, B₀ = 133 480.15 ± 0.12 and C₀ = 117 488.85 ± 0.16; for PD₃, B₀ = 69 471.10 ± 0.03 and C₀ = 58 974.37 ± 0.05. The effective ground-state values obtained for the bond angle and bond length are: for PH₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.420}{}_0$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.34}{}_5$; for PD₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.417}{}_6$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.35}{}_9$. The corresponding zero-point-average values were calculated to be: for PH₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4269}{}_9\text{± 0.0002}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.228}{}_7$; for PD₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4226}{}_5\text{± 0.0001}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.256}{}_7\text{± 0.004}$. For both species, the equilibrium values are $\text{r}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{) = 1.4115}{}_9\text{± 0.0006}$ and $\text{α}{}_{\mathrm{e}}\text{(}{}^{\mathrm{o}}\text{) = 93.32}{}_8\text{± 0.02}$.     

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°.     

Formaldehyde as a semirigid bender: The rotation-inversion spectrum in its Ã1A2 excited state

The semirigid bender Hamiltonian [Bunker and Landsberg, J. Mol. Spectrosc.67, 374–385 (1977)] was used to fit the rotation-inversion energy level separations in the $\text{A}\text{?}{}^1\text{A}{}_2$ excited state of formaldehyde. We fix the r⁰(CH) bond length and allow the R(CO) bond length and (H?H) bond angle to vary with the inversion angle ρ. The fit to 64 rotation-inversion energies (with v₄ and J < 4) is significantly better with a standard deviation of 0.199 cm^?1 than when the rigid bender [Bunker and Stone, J. Mol. Spectrosc.41, 310–332 (1972)] is used. The barrier height to planarity is 358 cm^?1 and the equilibrium ρ_e = 34.7°. The CO bond length is found to decrease by 0.034 from 1.3670 Å and the H?H angle by about 6 from 122.4° as the molecular configuration changes from planar to pyramidal. The rigid bender model developed earlier by Moule and Rao for formaldehyde [J. Mol. Spectrosc.45, 120–141 (1973)] is then used to fit the 32 rotation-(out-of-plane) bending energy levels (with v₄ = 0 and 1) of the $\text{X}\text{?}{}^1\text{A}{}_1$ ground electronic state of H₂CO. For this, a simple potential consisting of quadratic and quartic terms is used and the standard deviation of the fit is 0.148 cm^?1.     

Structure of cyclobutanone

The microwave spectra of the ¹⁸O and the α,α,α′,α′-tetradeuterated isotopic species of cyclobutanone have been investigated. Structural parameters determined are $\text{r}{}_{\mathrm{<mtext>CO</mtext>}}\text{= 1.204 ± 0.006}\text{A}\text{?}$, , ∠ H_αCH_α = 109.2 ± 1° with the methylene group tilted toward the carbonyl group by 4.6 ± 0.8°.     

Molecular structure of phosgene as studied by gas electron diffraction and microwave spectroscopy: The rz structure and isotope effect

The r_z structure of phosgene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: $\text{r}{}_{\mathrm{z}}\text{(}\text{CO}\text{) = 1.1785 ± 0.0026}\text{A}\text{?}$, $\text{r}{}_{\mathrm{z}}\text{(}\text{CCl}\text{) = 1.7424 ± 0.0013}\text{A}\text{?}$, ∠_z;ClCCl = 111.83 ± 0.11°, where uncertainties represent estimated limits of experimental error. The effective constants representing bond-stretching anharmonicity have been obtained from an analysis of the isotopic differences in the r_z structure: $\text{a}{}_3\text{(}\text{CO}\text{) = 2.9 ± 0.9}\text{A}\text{?}{}^{\mathrm{?1}}$, $\text{a}{}_3\text{(}\text{CCl}\text{) = 1.6 ± 0.4}\text{A}\text{?}{}^{\mathrm{?1}}$. The equilibrium bond distances have been estimated from the r_z structure for the normal species and from the anharmonic constants to be $\text{r}{}_{\mathrm{e}}\text{(}\text{CO}\text{) = 1.1756 ± 0.0032}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$.     

Microwave spectrum of the C4v molecule IF5 in the excited vibrational states v5(B1) = 1 and v9(E) = 1: Analysis of the ν5-ν9 Coriolis resonance

Measurements of the microwave spectrum of the C_4v molecule IF₅ in the excited vibrational states v₅(B₁) = 1 and v₉(E) = 1 are reported for the transitions J4 → 5, 5 → 6, 6 → 7, 8 → 9, and 9 → 10 (27–55 GHz). The Coriolis resonance interaction between these two states is analyzed by diagonalization of Hamiltonian matrices of dimension 3 × (2J + 1) in which all (Δl,Δk) = (±2, ±2)(q⁺), (±2, ±2)(q^?), and (0, ±4)(R₆) interactions are included as off-diagonal terms in addition to the v₅ = 1 ? v₉ = 1, l₉ = ±1(R₅₉) Coriolis interaction. In the v₉ = 1 state spectra, the $\text{B}{}_1\text{B}{}_2$l-doubling of the kl = ?1 transitions and $\text{A}{}_1\text{A}{}_2$ splittings of the kl = ?3 transitions and $\text{B}{}_1\text{B}{}_2$ splittings of the kl = +3 transitions, all enhanced by the Coriolis resonance, have been observed and measured. Least-squares refined rovibrational parameters for the v₅ = 1 and v₉ = 1 states are reported and a preliminary value for the rotational constant C₉ has been obtained.     

Infrared diode laser spectroscopy of the CF radical

The fundamental bands of the CF radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ 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 ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state, but also in ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, 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: B_e = 1.416 704 (37) cm^?1, α_e = 0.018 419 (50) cm^?1, $\text{r}{}_{\mathrm{e}}\text{= 1.271 977 (17)}\text{A}\text{?}$, D_e = 6.68 (15) × 10^?6cm^?1, p₀ = 0.008 580 (21) cm^?1, p₁ = 0.008 52 (11) cm^?1, and $\text{ν}{}_0\text{= 1286.1281 (5)}\text{cm}{}^{\mathrm{?1}}$, with three standard errors in parentheses.     

Microwave spectrum,torsional excitation energy,partial structure,and dipole moment of oxiranecarboxaldehyde

The microwave spectrum of oxiranecarboxaldehyde (glycidaldehyde) has been studied in the 8–40 GHz region. Transitions in the ground and first seven excited states of the torsional motion of the aldehyde group have been assigned for the species with the oxygen atom of the aldehyde group trans to the oxirane ring. The v = 0 to v = 1 torsional excitation energy is estimated to be 140 ± 10 cm^?1. The population of any other torsional conformer is less than 5% of the trans species at 200 K. Structural parameters were derived from rotational constants of the three singly substituted ¹³C species, whose spectra were observed in natural abundance. Substitution parameters are $\text{r}{}_{\mathrm{<mtext>CC</mtext>}}\text{(ring) = 1.453 ±0.025}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>CC</mtext>}}\text{(ald.) = 1.469 ± 0.010}\text{A}\text{?}$, ∠CCC = 119.8 ± 2.0°. The dipole moments determined by means of the Stark effect are μ_a = 1.932 ± 0.005 D, μ_b = 1.511 ± 0.017 D, and μ_c = 0.277 ± 0.156 D, with μ_t = 2.469 ± 0.031 D.     

Overtone bands of 14N16O and determination of molecular constants

The wavenumbers of the rotation-vibration lines of ¹⁴N¹⁶O are reported for the (2-0) and (3-0) bands. The full set of spectroscopic constants for the three bands (1-0), (2-0), and (3-0) has been determined with the method developed by Albritton, Schmeltekopf, and Zare for merging the results of separate least-squares fits. The vibrational constants ω_e, ω_ex_e, ω_ey_e, and the vibrational dependence of the rotational constants have been deduced. The apparent spin-orbit constant $\text{A}\text{?}{}_{\mathrm{<mtext>v</mtext>}}$ and its centrifugal correction $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext>}}$ (including the spin-rotation constant) have a vibrational dependence of the following form: $\text{A}\text{?}{}_{\mathrm{v}}\text{=}\text{A}\text{?}{}_{\mathrm{e}}\text{? α}{}_{\mathrm{A}}\text{(v +}\text{1}\text{2}\text{) + γ}{}_{\mathrm{A}}\text{(v +}\text{1}\text{2}\text{)}{}^2$ and $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>v</mtext>}}\text{=}\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>e</mtext>}}\text{? β}{}_{\mathrm{A}}\text{(v +}\text{1}\text{2}\text{) + δ}{}_{\mathrm{A}}\text{(v +}\text{built+1}\text{2}\text{)}{}^2$; the values of the constants in these two equations have been determined.     

l-type doubling transitions in Δ states of OCS

Molecular beam electric resonance spectroscopy has been used to measure the l-type doubling transitions in carbonyl sulfide. Transitions in J = 4 to J = 20 have been observed for the (02²0) vibrational state and for J = 1 and J = 2 for the (03¹0) state. The data has been analyzed to give the v = 2 energy separation $\text{E}{}_{\mathrm{<mtext>\Delta </mtext>}}{}^0\text{- E}{}_{\mathrm{<mtext>\Sigma </mtext>}}{}^0\text{= ?5.7861(2) + 8.36(1) × 10}{}^{\mathrm{?5}}\text{J(J + 1)}\text{cm}{}^{\mathrm{?1}}$, and the vibrational dependence of q to be 86.52(9)(v₂ + 1) KHz. The dipole moment of the (02²0) vibrational state is 0.6936(3) D.     

Thioformaldehyde: Rotational analyses of the Ã1A2-X̃1A1 visible absorption system

The $\text{A}\text{?}{}^1\text{A}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ electronic absorption spectra of CH₂S and CD₂S have been photographed under high resolution. Selected bands have been rotationally analyzed by least squares line fitting and by band contour methods. Improved rotational constants have been obtained for the ground states of CH₂S and CD₂S by use of combination differences. Bands of all three polarizations appear in the electronic spectrum. The type A origin band is magnetic dipole allowed, whereas the 4₀¹ band is type B. Perturbations are identified in the 0₀⁰ and 3₀¹4₀³ bands of CH₂S. The rotational constant A in the upper state decreases rapidly, in accordance with theoretical calculations, as successive quanta of the inversion mode ν′₄ are excited. The planar inertial defect has a small positive value in the zero level of the upper state although the molecule is slightly nonplanar; the r₈ geometry is $\text{r(}\text{CH}\text{) = 1.082}\text{A}\text{?}$, $\text{r(}\text{CS}\text{) = 1.701}\text{A}\text{?}$, angle HCH = 120°, and the out-of-plane angle is approximately 10°.     

Rotationally resolved infrared-ultraviolet double resonance spectroscopy in molecular D2CO and HDCO

Rotationally resolved infrared-ultraviolet double resonance (IRUVDR), consisting of sequentially excited rovibrational and rovibronic transitions sharing a common intermediate molecular level, is demonstrated. The technique employs pulsed CO₂ and tunable dye lasers and is applied to the molecules D₂CO and HDCO. For D₂CO, infrared pumping produces 100fold population enhancement in specific rotational sublevels of the v₄ = 1 level of the $\text{X}\text{?}{}^1\text{A}{}_1$ electronic ground state, followed by ultraviolet excitation in the 365-nm 4₁⁰ band of the $\text{A}\text{?}{}^1\text{A}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1$ electronic system. This ultraviolet excitation occurs at a specific set of dye laser frequencies, determined by the preceding rovibrational transition, and is detected by molecular fluorescence in the visible region. Similar effects observed in HDCO involve rovibrational pumping to either the v₆ = 1 or v₅ = 1 levels and give rise to enhanced rovibronic transitions in the 6₁⁰ and 5₁⁰ bands of the $\text{A}\text{?}\text{←}\text{X}\text{?}$ system, respectively. The resulting IRUVDR spectra enable detailed spectroscopic assignments to be made and are consistent with previous results from infrared and ultraviolet absorption, laser Stark, and infrared-radiofrequency double resonance spectroscopy. Collision-induced satellite structure, arising from rotational relaxation of the intermediate rovibrational level in the IRUVDR sequence, is also reported.     

Observation of the v = 0–13 levels of Na2b3Πu by OODR 3Λg-b3Πu fluorescence spectroscopy

The absolute vibrational numbering of the Na₂b³Π_u state has been established by direct observation of the v = 0–13 levels. These b³Π_u levels appear as the lower levels in rotationally resolved fluorescence spectra resulting from OODR excitation of ³Π_g, ³Δ_g, and ³Σ_g⁺ states via b³Π_u ～ A¹Σ_u⁺ mixed intermediate levels. The molecular constants for the Na₂b³Π_u state are (in cm^?1, one standard error in parentheses)

     

17.

On the electronic spectrum of the Mo₂ molecule observed after flash photolysis of Mo(CO)₆     

Yu.M Efremov  A.N Samoilova  V.B Kozhukhovsky  L.V Gurvich 《Journal of Molecular Spectroscopy》1978,73(3):430-440

Absorption and emission spectra of Mo₂ were investigated using flash photolysis of the Mo(CO)₆ molecule. Tentative vibrational and rotational analyses of the ⁹⁸Mo₂ spectra were performed. For the ground state, ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ type was proposed with ω_e = 477.1 cm^?1, $\text{r}{}_{\mathrm{e}}\text{= 1.929}\text{A}\text{?}$, and D₀(Mo₂) = 95 ± 15 kcal mole^?1. The results were compared with theoretical calculations for Mo₂ and experimental results for Cr₂ obtained previously. It seems reasonable that the transition metal diatomic molecules of this type have a high bond order.     

18.

Infrared diode laser spectroscopy of the NS radical     

Keiji Matsumura  Kentarou Kawaguchi  Keiichi Nagai  Chikashi Yamada  Eizi Hirota 《Journal of Molecular Spectroscopy》1980,84(1):68-73

The v = 1 ← 0 vibration-rotation bands of the NS radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ 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 $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$. The rotational and centrifugal distortion constants and the internuclear distance in the X²Π electronic state were obtained as follows: B_e = 0.775549(10) cm^?1, D_e = 0.00000129(33) cm^?1, and $\text{r}{}_{\mathrm{e}}\text{= 1.49403(4)}\text{A}\text{?}$, with three standard deviations indicated in parentheses.     

19.

Microwave spectrum and structure of cyanamide: Semirigid bender treatment     

Ronald D Brown  Peter D Godfrey  Burkhard Kleibömer 《Journal of Molecular Spectroscopy》1985,114(2):257-273

An extensive study of the microwave spectrum of cyanamide has been undertaken, the analysis being based in part on semirigidbender calculations by the methods of Bunker and Szalay. Inversion lines of NH₂CN, $\text{K}{}_{\mathrm{?1}}\text{= 2}{}^{\mathrm{a}}\text{Q}$ branches and a number of vibrational satellites of the J = 2?1 transition were observed. A two-vibrational-state Hamiltonian was used to fit simultaneously the 0⁺ and 0^? microwave data and yielded rotational constants X, Y, Z, D_J, D_JK, d₁, H_JK as well as the inversion splitting and the μ_yz-connecting matrix element. Vibrational satellite data of seven isotopic species and infrared frequencies of NH₂CN were included in the semirigid bender calculations: The NCN spine is nonlinear by ca. 5° in the equilibrium structure of the molecule. Also, $\text{r}{}_{\mathrm{<mtext>NH</mtext>}}\text{A}\text{?}\text{= 0.9994 + 0.0144?}{}^2$; <HNH/2 = 60.39° ? 0.1134?²; $\text{r}{}_{\mathrm{<mtext>NC</mtext>}}\text{A}\text{?}\text{= 1.3301 + 0.0327?}{}^2$ (? is the inversion angle in rad); $\text{r}{}_{\mathrm{<mtext>CN</mtext>}}\text{= 1.1645}\text{A}\text{?}$ fixed. The inclusion of the NC bond flexing was necessary in order to reproduce the observed vibrational satellite patterns of NH₂CN, NHDCN, and ND₂CN. The barrier to inversion of the amino group is 510 ± 6 cm^?1 with minima at ±45.0 ±0.2°. The inversion dipole moment is 0.91 ± 0.02 Debye.     

20.

Oscillator strengths in the Cameron system of carbon monoxide     

G.M. Lawrence  S.C. Seitel 《Journal of Quantitative Spectroscopy & Radiative Transfer》1973,13(8):713-716

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, $\text{?}{}_{00}\text{= (1.62±0.07) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{10}\text{= (1.96±0.09) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{20}\text{= (1.41±0.04) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{\mathrm{3\; 0}}\text{= (0.72±0.03) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{40}\text{= (0.31±0.02) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{50}\text{= (0.14±0.01) × 10}{}^{\mathrm{?7}}$. 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.     

$\text{T}{}_{\mathrm{e}}$	13 517.2 (1.3)	$\text{B}{}_{\mathrm{e}}$	0.1434 (0.0027)
$\text{ω}{}_{\mathrm{e}}$	153.6 (1.1)	$\text{α}{}_{\mathrm{e}}$	9×10?5 (4×10?4)
$\text{ω}{}_{\mathrm{e}}\text{ξ}{}_{\mathrm{e}}$	0.47 (0.09)	$\text{r}{}_{\mathrm{e}}$	3.20 (0.03) Å
$\text{A}{}_{\mathrm{e}}$	7.85 (0.60)	$\text{α}{}_{\mathrm{A}}$	0.19 (0.16)

On the electronic spectrum of the Mo2 molecule observed after flash photolysis of Mo(CO)6

Absorption and emission spectra of Mo₂ were investigated using flash photolysis of the Mo(CO)₆ molecule. Tentative vibrational and rotational analyses of the ⁹⁸Mo₂ spectra were performed. For the ground state, ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ type was proposed with ω_e = 477.1 cm^?1, $\text{r}{}_{\mathrm{e}}\text{= 1.929}\text{A}\text{?}$, and D₀(Mo₂) = 95 ± 15 kcal mole^?1. The results were compared with theoretical calculations for Mo₂ and experimental results for Cr₂ obtained previously. It seems reasonable that the transition metal diatomic molecules of this type have a high bond order.     

Infrared diode laser spectroscopy of the NS radical

The v = 1 ← 0 vibration-rotation bands of the NS radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ 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 $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$. The rotational and centrifugal distortion constants and the internuclear distance in the X²Π electronic state were obtained as follows: B_e = 0.775549(10) cm^?1, D_e = 0.00000129(33) cm^?1, and $\text{r}{}_{\mathrm{e}}\text{= 1.49403(4)}\text{A}\text{?}$, with three standard deviations indicated in parentheses.     

Microwave spectrum and structure of cyanamide: Semirigid bender treatment

An extensive study of the microwave spectrum of cyanamide has been undertaken, the analysis being based in part on semirigidbender calculations by the methods of Bunker and Szalay. Inversion lines of NH₂CN, $\text{K}{}_{\mathrm{?1}}\text{= 2}{}^{\mathrm{a}}\text{Q}$ branches and a number of vibrational satellites of the J = 2?1 transition were observed. A two-vibrational-state Hamiltonian was used to fit simultaneously the 0⁺ and 0^? microwave data and yielded rotational constants X, Y, Z, D_J, D_JK, d₁, H_JK as well as the inversion splitting and the μ_yz-connecting matrix element. Vibrational satellite data of seven isotopic species and infrared frequencies of NH₂CN were included in the semirigid bender calculations: The NCN spine is nonlinear by ca. 5° in the equilibrium structure of the molecule. Also, $\text{r}{}_{\mathrm{<mtext>NH</mtext>}}\text{A}\text{?}\text{= 0.9994 + 0.0144?}{}^2$; <HNH/2 = 60.39° ? 0.1134?²; $\text{r}{}_{\mathrm{<mtext>NC</mtext>}}\text{A}\text{?}\text{= 1.3301 + 0.0327?}{}^2$ (? is the inversion angle in rad); $\text{r}{}_{\mathrm{<mtext>CN</mtext>}}\text{= 1.1645}\text{A}\text{?}$ fixed. The inclusion of the NC bond flexing was necessary in order to reproduce the observed vibrational satellite patterns of NH₂CN, NHDCN, and ND₂CN. The barrier to inversion of the amino group is 510 ± 6 cm^?1 with minima at ±45.0 ±0.2°. The inversion dipole moment is 0.91 ± 0.02 Debye.     

Oscillator strengths in the Cameron system of carbon monoxide

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, $\text{?}{}_{00}\text{= (1.62±0.07) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{10}\text{= (1.96±0.09) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{20}\text{= (1.41±0.04) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{\mathrm{3\; 0}}\text{= (0.72±0.03) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{40}\text{= (0.31±0.02) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{50}\text{= (0.14±0.01) × 10}{}^{\mathrm{?7}}$. 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.