The a-X electronic band system of selenium monoxide at 1.8 μm

The emission spectrum of the SeO molecule excited in a microwave discharge and recorded at low resolution revealed the existence of a brief band system in the near-infrared region 6470-5560 cm^?1. The system consists of five bands divided into two groups which were assigned as the Δv = 0 and +1 sequences of the transition a2-X₂1 (X being the case ?c³Σ^? ground state). An approximate value of the rotational constant B₀ of state a was obtained from the observed separation between the Q and R heads of the 0-0 band and the known value of B₀ of state X. The derived molecular parameters of state a are: ν₀₀ = 5566.2 cm^?1, $\text{Δ}\text{G(}\text{1}\text{2}\text{) = 833.3}\text{cm}{}^{\mathrm{?1}}$, B₀ = 0.45₆ cm^?1.     

A new electronic band system of PbO

The chemiluminescence spectrum of atomic Pb reacting with O₃ under single-collision conditions includes a series of 55 bands in the regions 450–850 nm. A vibrational analysis is obtained which shows emission is to the ground state of PbO from excited electronic states not previously analyzed. Forty-nine of the bands are assigned to the a(1)-X(0⁺) transition and the remaining six are tentatively identified as the forbidden b(0^?)-X(0⁺) transition. Both the a and b states are believed to be Hund's case (c) components of the ³Σ⁺ states arising from the configuration $\text{σ}{}^2\text{π}{}^3\text{π}{}^1$. The vibrational parameters of the a state are ν₄ = 16 029 ± 8, ω_e′ = 478.7 ± 1.9, and ω_ex_e′ = 2.292 ± 0.128 cm^?1, where the uncertainties represent two standard deviations of the least-squares fit. Emission is also observed from the PbO B state produced in the reaction of metastable Pb atoms with O₃. Using pulsed laser excitation, an attempt is made to determine radiative lifetimes. We find for the PbO A(0⁺) state τ = 3.74 ± 0.3 μsec, and for the PbO B(1) state τ = 2.58 ± 0.3 μsec, while for the a(1) state τ is estimated to be greater than 10 μsec. From the vibrational analysis, energy conservation arguments place a lower limits to the ground state dissociation energy of $\text{D}{}_0{}^0\text{(}\text{PbO}\text{) ≥ 3.74 ± 0.03}\text{eV}$ (86.2 ± 0.7 kcal/mole). For the Pb + O₃ reaction we find less than 1% of the products are PbO¹ molecules that emit in the visible. Correlations are made with the low-lying states of other Group IV chalconides based on the assignment of the PbO $\text{a}{}^3\text{Σ}{}^{\mathrm{+}}\text{(1)}$ state and the correspondence between the low-lying triplet states of PbO and CO.     

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°.     

Doppler-limited dye laser excitation spectroscopy of HCCl

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^1\text{A″(050) ←}\text{X}\text{?}{}^1\text{A′(000)}$ vibronic band of HCCl was observed between 16 539 and 16 656 cm^?1 with the Doppler-limited resolution, 0.03 cm^?1. The HCCl molecule was generated by the reaction of discharged CF₄ with CH₃Cl. The observed spectra were assigned to c-type transitions with ΔK_a = ±1 and also to axis-switching transitions with ΔK_a = 0 or ?2, but all with K′_a = 0, both for HC³⁵Cl and HC³⁷Cl. A rotational analysis yielded the rotational constants and quartic centrifugal distortion constants for the ground vibronic state and the band origin. A weak vibronic band, about one-third as intense as the main band, was found at about 57 cm^?1 to the violet of the main band for both isotopic species, and was ascribed to a transition from the ground vibronic state to a vibrational level, possibly (041), of the à state. The rotational levels of HC³⁵Cl in the à state showed a large perturbation; the J′ = 8, 9, and 10 levels were found to be split into two components. A normal coordinate analysis was carried out to calculate the centrifugal distortion constants and the inertia defect, which were in fair agreement with the observed values. The molecular structure of HCCl in the ground vibronic state was recalculated from the rotational constants of the two isotopic species combined with the 0.75B₀ + 0.25C₀ value previously reported for DC³⁵Cl.     

The rotational spectrum of the X 2Σ+ state of the SrF radical using laser microwave optical double resonance

The pure rotational spectrum of the $\text{X}{}^2\text{Σ}{}^{\mathrm{+}}$ state of the gaseous SrF radical has been measured using microwave optical double resonance (MODR) techniques. The analysis fully confirms the recent dye laser excitation spectrum and rotational assignment of the $\text{B}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Σ}{}^{\mathrm{+}}$ system. Transitions were measured in both the v″ = 0 and v″ = 1 states to give values of B_e″ = 0.250533 cm^?1, α_e″ = 1.546 × 10^?3 cm^?1 and γ″ (spin-rotation) = 2.49 × 10^?3 cm^?1. General qualitative features of MODR in ²Σ⁺ states are treated and suggested improvements for obtaining experimental hyperfine constants are discussed. The more precise ground state constants are merged with the B-X optical analysis to obtain a more accurate set of constants for both states.     

Doppler-limited dye laser excitation spectroscopy of HCF

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^1\text{A″(000) ←}\text{X}\text{?}{}^1\text{A′(000)}$ vibronic band of HCF was observed between 17 188 and 17 391 cm^?1 with the Doppler-limited resolution, 0.04 cm^?1. The HCF molecule was produced by the reaction of discharged CF₄ with CH₃F, and 853 lines were observed, of which 516 transitions were assigned to K′_a ← K″_a = 3 ← 4, 2 ← 3, 1 ← 2, 0 ← 1, 1 ← 0, 2 ← 1, 0 ← 0, 1 ← 1, 2 ← 2, 3 ← 3, 2 ← 0, and 0 ← 2 subbands. A rotational analysis yielded the rotational constants and quartic and sextic centrifugal distortion constants for both the $\text{A}\text{?}$ and $\text{X}\text{?}$ states and the band origin, with good precision. The molecular constants determined reproduce the observed transition frequencies with an average deviation of 0.0038 cm^?1. Small rotational perturbations in the excited state were found at J = 5, 6 and J = 10, 11 of J_1,J and at J = 15, 16 of J_2,J?1 levels.     

Rotational analyses and vibrational assignments of the 463- and 474-nm bands of NO2

The excitation spectrum of NO₂ was investigated in the blue region by using a Nd:YAG laser-pumped dye laser. The 463- and 474-nm bands of the ²B₂-²A₁ system were identified and analyzed using the simplification that occurs if the excitation spectrum is monitored at particular wavelengths. Band origins and rotational constants were obtained. Vibrational assignments have been given to these bands by comparing the Franck-Condon Factors calculated for the ²B₂-²A₁ system with the fluorescence intensities of bands going to different vibrational levels of the ground state. The vibrational assignments and molecular constants obtained in this work are (v′₁, v′₂, v′₃) = (3, 11, 0)ν₀(K′ = 0) = 21584.1, $\text{B}\text{= 0.405}$, and $\text{∥}\text{?}\text{′∥ = 0.05}\text{cm}{}^{\mathrm{?1}}$ for the 463-nm band; and (v′₁, v′₂, v′₃) = (2, 12, 0), ν₀(K′ = 1) = 21104.9, $\text{B}\text{= 0.408}$, and $\text{∥}\text{?}\text{′∥ = 0.03}\text{cm}{}^{\mathrm{?1}}$ for the 474-nm band.     

Noble gas halides: The B → X and D → X systems of 136Xe35Cl

The B → X (2870–3100 Å) and D → X (2250–2370 Å) band systems of ¹³⁶Xe³⁵Cl are photographed and vibrationally analyzed. A simultaneous least-squares fit of 41 band-heads in the B-X system and 35 in D-X yields, in part, the following constants (in cm^?1): T_eB = 32 405.8, T_eD = 42 347.9, ω_eB = 194.75, ω_eD = 204.34, ω_eX = 26.22. The ground state dissociation energy ($\text{D}$″_e) is estimated to be 281 ± 10 cm^?1. Potential curves are derived for all three states through Franck-Condon calculations. From these curves the D-state internuclear distance is 0.09 ± .02 Å smaller than the B-state distance.     

Reexamination of the I2 spectrum near the B(3Π0u+) state dissociation limit

The disagreement of Danyluk and King's (Chem. Phys.25, 343 (1977)) rotational constants for levels lying near the dissociation limit of B-state I₂ with the mechanical behavior predicted by near-dissociation theory is investigated. The discrepancies are shown to be much too large to be explained by either the neglect of centrifugal distortion effects in the original analysis or by rotational or spin-rotation coupling to a nearby repulsive 1_u state. These differences are therefore attributed to experimental error, a conclusion which is confirmed by more recent experimental results. A reanalysis of the best available data for levels near the dissociation limit of B-state I₂ then yields improved values for the B-state dissociation limit $\text{D}$ = 20 043.16 (±0.02) cm^?1 of the vibrational index at dissociation v_$\text{D}$ = 87.32 (±0.04) and of the long-range potential constant $\text{C}{}_5\text{= 2.88 (±0.03) × 10}{}^5\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^5$. This in turn implies a slightly improved ground-state dissociation energy of $\text{D}$₀ = 12 440.18 (±0.02) cm^?1.     

High resolution Raman spectroscopy of gases with laser sources. The rotational spectrum of cyanuric fluoride-C3N3F3

The pure rotational Raman spectrum of cyanuric fluoride vapor was photographed using a high resolution plane grating spectrograph. The spectrum was excited with the $\text{λ = 4880}\text{A}\text{?}$ radiation emitted by a single-mode argon-ion laser. Two sets of molecular constants were determined from the R and S branches. The preferred results are those determined from the S-branch data. These are: B₀ = 0.0655954 ± 14 × 10^?7 cm^?1, D_J = (2.52 ± 0.17) × 10^?9 cm^?1 and H_J = (?1.59 ± 0.59) × 10^?14 cm^?1, where the uncertainties are one standard deviation. Possible effects of line shifts due to unresolved K structure and the presence of hot bands on the accuracy of the values of the molecular constants are discussed. The B₀ value is compared to the rotation constant computed with the structural parameters determined with the electron diffraction technique; the agreement between these two rotation constants is only fair.     

Laser-induced fluorescence spectrum of nitrogen dioxide in the neighborhood of 6125 Å

The resonance fluorescence spectrum of nitrogen dioxide has been excited by a tunable, cw dye laser in the neighborhood of 6125 Å. The rotational constants of the ²B₂ upper electronic state are determined as follows, in units of cm^?1: A_v′ = 7.2 ± 0.6; $\text{B}\text{?}{}_{\mathrm{v}}\text{′ = 0.454 ± 0.015}$; B_v′ = 0.496 ± 0.046; C_v′ = 0.412 ± 0.019. The band origin is at 16 325.1 ± 1.8. Quoted error limits are standard deviations obtained from the fit of the data. The vibrational assignment of the upper state is (0, 5, 0), and by combination with the data of other workers, we estimate for its vibrational constants, in cm^?1: ω₁′ + x₁₁′ = 1425.7; ω₂′ = 876.6; x₂₂′ = ?0.83; x₁₂′ = ?8.1. The molecular geometry in the upper state is briefly discussed.     

The D′ → A′ transition in Br2

A vibrational and rotational analysis is presented for the D′ → A′ transition (2800–2950 Å) of Br₂. The analysis includes 11 rotationally analyzed bands for ⁷⁹Br₂ and 3 for ⁸¹Br₂, plus bandheads for 70 additional v′-v″ bands of ⁷⁹Br₂, ⁸¹Br₂, and ⁷⁹Br⁸¹Br. The latter include some violet-degraded and spikelike features at the long-wavelength end of the spectrum, which are interpreted and assigned with the aid of band profile simulations. The assigned features are fitted directly to 14 vibrational and rotational expansion parameters for the two electronic states, from which the following spectroscopic constants are obtained: ΔT_e = 35706 cm^?1, ω′_e = 150.86 cm^?1, ω″_e = 165.2 cm^?1, B′_e = 0.042515 cm^?1, B″_e = 0.05944 cm^?1, $\text{R′}{}_{\mathrm{e}}\text{= 3.170}\text{A}\text{?}$, $\text{R″}{}_{\mathrm{e}}\text{= 2.681}\text{A}\text{?}$. The spectroscopic parameters are used to calculate RKR potentials and Franck-Condon factors for the transition.     

The characterization of the complete set of bound vibronic states of HNO in its excited Ã1A″ electronic state

Laser-induced fluorescence excitation spectra of the HNO $\text{A}\text{?}{}^1\text{A″-}\text{X}\text{?}{}^1\text{A′}$ band system have been recorded with high sensitivity. This has enabled detection of the Franck-Condon unfavored vibronic bands (002)-(000) and (003)-(000), thereby completing the set of fully bound vibronic levels in the $\text{A}\text{?}$ state. Extensions have also been made to other bands. A strong Coriolis resonance between the K_a¹ = 8 levels of the excited (010) vibronic state and the K_a¹ = 9 levels of the (001) state leads to rotational perturbations of up to 9 cm^?1. The (100-000) band includes weak axis-tilting branches. It is concluded from the vibrational energy level spacings that vibronic interaction makes an important contribution to the energies of the higher bending levels, consistent with the correlation of the $\text{A}\text{?}{}^1\text{A″}$ state with a component of a ¹Δ state for linear HNO.     

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.     

Far-infrared laser magnetic resonance spectra of the PH and PD radicals in X3Σ−

Far-infrared laser magnetic resonance (LMR) spectra of PD in the ground vibronic state (X³Σ^?, v = 0) were observed using the 570.6-, 380.6-, 287.3-, 232.9-, 191.6-, and 164.6-μm laser lines as sources, and the v = 1 spectrum was also observed with the 392.1-μm laser line. By combining the present results with mid-infrared LMR and optical spectroscopic data already reported, the molecular constants of PD in X³Σ^? were refined as follows: B₀ = 4.362 8675(77), D₀ = 0.000 118 03(24), λ₀ = 2.208 48(57), γ₀ = ?0.039 900(34), B₁ = 4.269 248(65), λ₁ = 2.209 5(10), γ₁ = ?0.038 82(21), and ν₀ = 1653.284 91(51), all in cm^?1 with 3σ in parentheses. The ³¹P hyperfine coupling constants were determined to be α_P = 0.004 330(39) and β_P = ?0.005 312(32) for the v = 0 state and α_P = 0.004 66(40) and β_P = ?0.004 79(69) for the v = 1 state, again in cm^?1 with 3σ in parentheses. The far-infrared LMR spectra of PH in the X³Σ^?, v = 0 state were measured on five new laser lines, and an analysis of the observed spectrum combined with that already reported yielded molecular constants much improved in precision. Using the results on both PD and PH, the equilibrium structure and the potential constants up to the fourth order were derived, where allowance was made for adiabatic and nonadiabatic corrections: $\text{r}{}_{\mathrm{e}}{}^{\mathrm{BO}}\text{= 1.42140(22)}\text{A}\text{?}$, ω_e(PH) = 2366.79(16) cm^?1, a₁ = ?2.3797(18), and a₂ = 3.461(14).     

Vibration-rotation spectrum of HCF (X̃1A′) by laser-induced fluorescence

The vibration-rotation spectrum of the HCF molecule was observed by laser-induced fluorescence with an Ar⁺ laser. The laser line of 514.5 nm coincided with two rovibronic transitions, ^rR₁(9) and ^pQ₅(9) for $\text{A}\text{?}{}^1\text{A″(020)-}\text{X}\text{?}{}^1\text{A′(000)}$. The spectrum consisted of the progression of bending vibrational mode ν₂. The rotational lines were fully resolved for each of the vibronic bands. The analysis yielded the vibrational and rotational parameters for both the ground and the excited vibronic states. The rotational parameters of the $\text{X}\text{?}{}^1\text{A′}$ state were obtained for four vibrational levels [(0v₂0), v₂ = 0 – 3].     

Rotational analysis and radiative lifetime measurement on the 2B1 (K′ = 0) excited state of NO2 with v′2 = 6, 7, 8, and 9

The rotational structure of the ²B₁ (K′ = 0) subbands of NO₂ with v′₂ = 6, 7, 8, and 9 were analyzed by means of the time-gated excitation spectrum. The excitation spectrum monitored at ν₂, 2ν₂, or 3ν₂ fluorescence band was fairly simplified in comparison to its corresponding absorption spectrum. The band origins and rotational constants are evaluated from the observed data: ν₀ = 20205.0 cm^?1, $\text{B}\text{′ = 0.374}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 6; ν₀ = 21104.4 cm^?1, $\text{B}\text{′ = 0.374}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 7; ν₀ = 22001.9 cm^?1, $\text{B}\text{′ = 0.375}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 8ν₀ = 22898.0 cm^?1, $\text{B}\text{′ = 0.375}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 9. The value of $\text{B}\text{′}$ extrapolated to v′ = 0 is 0.370 cm^?1. This value corresponds to the bond length of 1.19 Å. Fluorescence decays of these excited levels were also studied. Radiative lifetimes obtained by extrapolation to zero pressure from the $\text{1}\text{τ}\text{– P}$ plots were 25–40 μsec. The short-lived excited levels previously reported by some authors were not found.     

The laser magnetic resonance spectrum of the NCO radical at 5.2 μm

Lines in the ν₃ (“antisymmetric” stretch) fundamental of the NCO radical in the $\text{X}\text{?}{}^2\text{Π}$ state were studied by CO laser magnetic resonance. The observations were assigned to P and R lines in the vibration-rotation band and lead to a precise determination of the vibrational interval and the anharmonic correction to the rotational constant: ν₃ = 1920.60645(19) cm^?1, α₃ = 0.003338(21) cm^?1. A single transition in the hot band (011)-(010), ${}^2\text{Δ}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Δ}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ was detected. This observation is used to determine the origin of the hot band as 1907.11892(20) cm^?1, i.e., the anharmonicity parameter x₂₃ = ?13.48753(28) cm^?1.     

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.     

Doppler-limited dye laser excitation spectroscopy of the DSO radical

The $\text{A}\text{?}{}^2\text{A′(003) ←}\text{X}\text{?}{}^2\text{A″(000)}$ vibronic transition (16 370 to 16 425 cm^?1) of the DSO radical in studied by Doppler-limited dye laser excitation spectroscopy. DSO is produced in a flow system by reacting the products of a microwave discharge in O₂ with D₂S. About 637 observed lines are assigned to 987 transitions of the 19 subbands: K′_a ← K″_a = 6 ← 5, 5 ← 4, 4 ← 3, 3 ← 2, 2 ← 1, 1 ← 0, 0 ← 1, 1 ← 2, 2 ← 3, 3 ← 4, 0 ← 0, 1 ← 1, 2 ← 2, 3 ← 3, 4 ← 4, 3 ← 1, 2 ← 0, 0 ← 2, and 1 ← 3. They are analyzed to determine rotational constants, centrifugal distortion constants, and spin-rotation constants for both the ground and the excited electronic states. The band origin obtained is 16 413.874 (2.5σ = 0.002) cm^?1. The rotational constants determined are combined with the previous result on HSO (M. Kakimoto et al., J. Mol. Spectrosc.80, 334–350 (1980)) to calculate the structural parameters for this radical in both the states: $\text{r(}\text{SO}\text{) = 1.494(5)}\text{A}\text{?}$, $\text{r(}\text{SH}\text{) = 1.389(5)}\text{A}\text{?}$, and ∠HSO = 106.6(5)° for the $\text{X}\text{?}{}^2\text{A″}$ state, and $\text{r(}\text{SO}\text{) = 1.661(10)}\text{A}\text{?}$, $\text{r(}\text{SH}\text{) = 1.342(8)}\text{A}\text{?}$, and ∠HSO = 95.7(21)° for the $\text{A}\text{?}{}^2\text{A′(003)}$ state, where values in parentheses denote 2.5σ.