The 404.5-nm system of the ReO molecule

Observations on the emission spectrum of ReO in the region 375–870 nm are reported. Five bands of a $\text{ΔΩ}\text{= 0}$ system with (0, 0) band at 404.5 nm have been rotationally analyzed and the principal results for ¹⁸⁷ReO are (in cm^?1) ν₀ = 24 709.90, B′_e = 0.3819, B″_e = 0.4252, ω′_e = 874.8₂, and $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.1}{}_2$. Data on the minor isotopic species ¹⁸⁵ReO are also reported. It is suggested that broad rotational profiles found in bands near 842 nm may be due to nuclear hyperfine structure.     

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 visible and photographic infrared spectrum of osmium oxide

The emission spectrum of OsO has been photographed in the region 405–875 nm where many new bands have been observed. In favorable cases the ${}^{190}\text{OsO}{}^{192}\text{OsO}$ isotopic splittings have been resolved and aid in vibrational assignments. Three visible bands in the region 433–470 nm have been assigned as (1,0), (0,0), and (0,1) of a $\text{ΔΩ}\text{= 0}$ electronic transition. The (0,0) and (0,1) bands have been rotationally analyzed, yielding principal constants (cm^?1) for the visible system of ν₀ = 22 273.3, B′₀ = 0.3657, D′₀ = 2.8 × 10^?7, B″_e = 0.4023, D″_e = 3.2 × 10^?7, $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 780.7}$, and $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 884.9}$. A band at 825.4 nm has been found to be a $\text{ΔΩ}\text{= +1}$ (0,0) band with the same lower state as in the analyzed visible bands. Constants for the upper state of the ir system are ν₀ = 12 109.7, B′₀ = 0.3845, and D′₀ = 3.1 × 10^?7 cm^?1.     

The D′ → A′ transition in I2

A detailed vibrational analysis is given for the D′(2g) → A′(2u³Π) transition (3300–3460 Å) in I₂. The assignments include ～ 150 v′-v″ bands in ¹²⁷I₂ and ～100 in ¹²⁹I₂, spanning v′ levels 0–15 and v″ levels 4–30. These bands are mainly red-degraded but include some violet-degraded and line-like features. The analysis is corroborated by Franck-Condon and band profile calculations. The least-squares fit yields the following constants (cm^?1); ΔT_c = 30 340.8, ω′_e = 103.95, ω_eχ′_e = 0.206, ω″_e = 106.1, ω_eχ″_e = 0.81. Anomalous behavior in the vibrational level structure above v″ = 23 makes the extrapolation to the A′ dissociation limit uncertain, so the absolute energies of both states remain ill-defined. However there is a possibility that the D′ state is the state labeled α by King et al. [Chem. Phys. 56, 145–156 (1981)], in which case the energies are known precisely. There is evidence of weak emission from at least two other electronic transitions in this spectral region, probably $\text{D(0}{}^{\mathrm{+}}\text{u) → X(}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ ($\text{λ}\text{< 3300}\text{A}\text{?}$) and β → A(1u³Π) ($\text{λ}\text{> 3300}\text{A}\text{?}$).     

The B(2Σ+) → X(2Σ+) transition (4050–4500 Å) in Hgl

The B → X band system (4050–4500 Å) of HgI is photographed and vibrationally analyzed for the isotopically pure species ²⁰⁰Hg¹²⁷I and ²⁰⁰Hg¹²⁹I. The assigned bands span v″ levels 5–26 and v′ levels 0–13. The least-squares analysis indicates that the previously accepted v″ numbering for this system is one unit too high. Band-profile simulations and Franck-Condon calculations indicate that the internuclear separation (R′_e-R″_e) is 0.49 Å. The ground-state dissociation energy ($\text{D}$_e) is estimated to be 2750 ± 80 cm^?1. Spin splitting is found to contribute significantly to the band structure.     

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 the B3Π(0+) → X1Σ+ band systems of 35Cl35Cl and 35Cl37Cl in the chlorine afterglow emission spectrum

The B³Π(0⁺) → X¹Σ⁺ band system of Cl₂, excited by the recombination of ground state $\text{Cl}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ atoms at total pressures near 2 Torr, has been rotationally analyzed in the range 6300–9900 Å. About 30 bands, with 0 ≤ v′ ≤ 6 and 5 ≤ v″ ≤ 14, were investigated, mostly for both ³⁵Cl³⁵Cl and ³⁵Cl³⁷Cl. The band origins and rotational constants for the B state were obtained with the help of the known constants for the ground state. The principal molecular constants (cm^?1) for the B³Π(0⁺) state of ³⁵Cl³⁵Cl are as follows: T_e′ = 17 817.67(3); ω_e′ = 255.38(3); ω_e′x_e′ = 4.59(1); ω_e′y_e′ = ?0.038(8); D_e′ = 3341.17(14); B_e′ = 0.16313(3); α_e′ = 2.42(3) × 10^?3; γ_e′ = ?5.7(7) × 10^?5. The equilibrium internuclear separation is 2.4311(2) Å. The results of Briggs and Norrish on a transient absorption spectrum of Cl₂ assigned as $\text{0}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{← B}{}^3\text{Π}\text{(0}{}^{\mathrm{+}}\text{)}$ are reinterpreted with the present constants.     

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.     

The structure of the triethylenediamine molecule in an excited electronic state

Ultraviolet absorption spectrum has been observed of triethylenediamine (1,4 diazabicyclo[2.2.2]octane) ($\text{D}{}_{\mathrm{<mtext>3</mtext><mtext>A</mtext><mtext>?</mtext>}}$) vapor in the 2200–2600 Å region, and an analysis has been made of its vibrational structure. The vibronic 0-0 transition was determined to be at 2513.65 Å (39782.8 cm^?1), and in the 2540–2590 Å region there were four hot bands found: two from the a₁′-type vibrational levels and two from the a₂″-type vibrational levels of the ground electronic state. The fine structures of these hot bands were examined with 0.49 Å/mm dispersion (slit width = 50 μm). For each of the two a₂″-type hot bands, a progression with 30 ～ 40 cm^?1 spacings was observed; whereas, no such progressions were found for the a₁′-type hot bands, in which absorption peaks are much more concentrated within narrow ranges. These progressions were attributed to a large-amplitude twisting motion of triethylene-diamine molecule. For explaining the whole energy-level structure, another large-amplitude motion, has been postulated. That is a double-minimum deformation motion along the molecular axis; in each minimum, one of the two NC₃ umbrellas is half-way open and the other NC₃ umbrella is half-way closed. The height of the potential barrier between these two minima has been estimated to be 1586 cm^?1.     

The vacuum ultraviolet absorption spectrum of ClO

The flash photolysis of ClO₂ has yielded a new absorption spectrum of ClO in the vacuum ultraviolet. Six electronic transitions have been assigned and vibrational constants for the upper states are given. All of the transitions are Rydberg in nature. The first four of these transitions are thought to be ²Σ ← X²Π_i from which a spin-orbit coupling constant A = ?318 ± 5 cm^?1 is obtained for the ground state.Hot bands in three of the above systems of ClO have been observed in absorption. This has enabled the direct measurement of the ground state vibrational constant ($\text{Δ}\text{G}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{″ = 845 ± 4}\text{cm}{}^{\mathrm{?1}}$; ω_e″ = 859 cm^?1) for the first time.Extinction coefficients for a number of the ClO transitions have been measured.     

Fourier spectrometry: Rovibrational analysis of an infrared 1Π → 1Σ system of yttrium monoiodide

The infrared spectrum of yttrium monoiodide has been excited in an electrodeless microwave discharge and explored between 2500 and 12 000cm^?1 with a high-resolution Fourier transform spectrometer. A unique system is observed (ν₀₀ = 9905.520 cm^?1), which we attribute to a ${}^1\text{Π}\text{→}{}^1\text{Σ}$ transition and an extensive analysis is made. Rovibrational constants are obtained for both states mainly from a simultaneous multiband fitting. This procedure is applied to the whole set of 2231 observed line wavenumbers in the 1-0, 0-0, and 0–1 bands, yielding a final weighted standard deviation of 0.0038 cm^?1. Furthermore, a partial analysis of the 2-0 and 3-1 bands is performed. The following equilibrium constants are derived (cm^?1):

$\text{ω′}{}_{\mathrm{e}}\text{=192.210 ω′}{}_{\mathrm{e}}\text{x′}{}_{\mathrm{e}}\text{=0.463}$

$\text{B′}{}_{\mathrm{e}}\text{=0.0399133 α′}{}_{\mathrm{e}}\text{=0.0001150}$

$\text{ω″}{}_{\mathrm{e}}\text{=215.815 ω″}{}_{\mathrm{e}}\text{x″}{}_{\mathrm{e}}\text{=0.514}$

$\text{B″}{}_{\mathrm{e}}\text{=0.0422163 α″}{}_{\mathrm{e}}\text{=0.0001125}$

High-order constants D_v and H_v are also calculated for the various vibrational levels (v′ = 0, 1, 2, 3; v″ = 0, 1).     

The electronic isotope shift in the A2Π-X2Σ+ bands of BeH,BeD and BeT

The 0-0, 1-1, 2-2, and 3-3 bands of the A²Π-X²Σ⁺ transition of the tritiated beryllium monohydride molecule have been observed at 5000 Å in emission using a beryllium hollow-cathode discharge in a He + T₂ mixture. The rotational analysis of these bands yields the following principal molecular constants.

$\text{A}{}^2\text{Π:}\text{B}{}_{\mathrm{e}}\text{= 4.192}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.333}\text{A}\text{?}$

$\text{X}{}^2\text{Σ:}\text{B}{}_{\mathrm{e}}\text{= 4.142}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.341}\text{A}\text{?}$

$\text{ω}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″ = 16.36}\text{cm}{}^{\mathrm{?1}}\text{; ω}{}_{\mathrm{e}}\text{′X}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″X}{}_{\mathrm{e}}\text{″ = 0.84}\text{cm}{}^{\mathrm{?1}}$

From the pure electronic energy difference (E_Π - E_Σ)_BeT = 20 037.91 ± 1.5 cm^?1 and the corresponding previously known values for BeH and BeD, the following electronic isotope shifts are derived

$\text{ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?4.7 ≠ 1.5}\text{cm}{}^1\text{, ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?1.8 ≠ 1.5}\text{cm}{}^1$

and related to the theoretical approach given by Bunker to the problem of the breakdown of the Born-Oppenheimer approximation.     

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.     

Rotational analysis of the B2Σ+ → X2Σ+ system of the aluminum monoxide radical,AlO

Twenty-five bands of the B²Σ → X²Σ system of AlO with 0 ≤ v′ ≤ 9 and 0 ≤ v″ ≤ 6 have been photographed at high resolution. The measured positions of the assigned lines of each band have been fitted by least-squares to obtain estimates of the constants (B′, D′, B″, D″), the band origin, and Δγ_v′,v″, which is the difference of the upper and lower state spin-doubling constants (γ′_v and γ″_v). The parameters from individual bands have been merged to single-valued estimates, as well as to polynomial representations in ($\text{v +}\text{1}\text{2}$). Although the spin-doubling constants are not found absolutely for either state, their vibrational dependences are well determined. The data are employed in the computation of RKR potential energy curves and an array of Franck-Condon factors and r-centroids.     

The 2880-Å emission spectrum of I2: Ion-pair states near 47 000 cm−1

An emission system of I₂ in Ar in the region 2830–2890 Å is examined under high resolution and found to display fine violet-degraded band structure. This system is interpreted as a charge-transfer transition originating from an ion-pair state near 47 000 cm^?1 and terminating on a weakly bound state which dissociates to two ground-state atoms. This interpretation is supported by spectral simulations employing a bound-free model. The transition is tentatively assigned as $\text{0}{}_{\mathrm{<mtext>g</mtext>}}{}^{\mathrm{?}}\text{→ 2431 0}{}_{\mathrm{<mtext>u</mtext>}}{}^{\mathrm{?}}\text{(}{}^3\text{Π}\text{)}$, according to which the excited state becomes the fourth ion-pair state near 47 000 cm^?1 to be experimentally characterized, and the lower state is the last component of the lowest ³Π state to be identified. The vibrational assignments include about 45 bands in ¹²⁷I₂ and ¹²⁹I₂, spanning v′ = 0–4 and v″ = 6–19, but with the numbering of the lower state remaining uncertain by several units. The main spectroscopic constants for the excited state are T_e = 47 070 cm^?1, ?_e = 105.7 cm^?1, ?_ex_e = 0.49 cm^?1. The spectral simulations place the lower state's potential curve 34 650 cm^?1 below the upper state at R = R′_e, with slope ?850 cm^?1/Å. For our “best” numbering of the lower state, ?_e = 20.5 cm^?1, ?_ex_e = 0.29 cm^?1, T_e = 12 190 cm^?1, and D_e = 360 cm^?1.     

Analysis of the ν6(A″2) band of cyclopropane-d6 recorded under high resolution

The parallel band ν₆(A″₂) of C₃D₆ near 2336 cm^?1 has been studied with high resolution (Δν = 0.020 – 0.024 cm^?1) in the infrared. The band has been analyzed using standard techniques and the following parameters have been determined: B″ = 0.461388(20) cm^?1, D″_J = 3.83(17) × 10^?7 cm^?1, ν₀ = 2336.764(2) cm^?1, α^B = (B″ ? B′) = 8.823(12) × 10^?4 cm^?1, β^J = (D″_J ? D′_J) = 0, and α^C = (C″ ? C′) = 4.5(5) × 10^?4 cm^?1.     

Variation of electronic transition moment with the internuclear separation for the (AO+−X1Σ+) band system of PbO

Relative integrated intensities of the (AO⁺?X¹Σ⁺) band system of PbO have been measured by photographic photometry. These have been interpreted with the aid of Franck-Condon factors (q_υ′υ″) and r-centroids ($\text{r}{}_{\mathrm{\upsilon \prime \upsilon ″}}$) to show that the variation of electronic transition moment with internuclear separation is R_e(r)=const.(0.521r?1). Arrays are shown for the band strengths S_υ′υ″.     

The E → B transition (3000–3140 Å) in Br2

The region 3030–3140 Å of the emission spectrum of Br₂ is reinvestigated using sources containing separated ⁷⁹Br₂ and ⁸¹Br₂. The analysis, which spans v′ levels 0–15 and v″ levels 8–31, indicates that the transition in this region is the analog of the E → B system in I₂, and it is so redesignated. The following spectroscopic constants are obtained for the E state of ⁷⁹Br₂: T_e = 49 779.06 cm^?1, ω_e = 150.46 cm^?1, ω_eχ_e = 0.383 cm^?1, B_e = 0.04172 cm^?1, $\text{R}{}_{\mathrm{e}}\text{= 3.20}\text{A}\text{?}$.     

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.     

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.