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.     

Diode laser spectroscopy of the CCl radical

Vibration-rotation transitions of the fundamental band have been observed for both C³⁵Cl and C³⁷Cl in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ states by using an infrared diode laser spectrometer with Zeeman modulation. A few lines of the “hot” band (v = 2 ← 1) have also been recorded for C³⁵Cl. From an analysis of the observed spectra improved values were obtained for the vibrational harmonic frequency and anharmonicity constant, rotational constants, and Λ-doubling parameters. It was found necessary to take into account centrifugal distortion effects on the spin-orbit coupling constant A in the analysis, which gave $\text{(}\text{dA}\text{dr}\text{)}{}_{\mathrm{<mtext>e</mtext>}}\text{r}{}_{\mathrm{<mtext>e</mtext>}}$ to be ?176 ± 38 or ?125 ± 38 cm^?1, depending upon whether ²Σ^? or ²Σ⁺ states contribute more to the Λ-type doubling. The equilibrium internuclear distance r_e was calculated from the derived rotational constants to be 1.64506 ± 0.00016 Å.     

Microwave spectrum of 35ClO in the excited vibrational state and a comment on the centrifugal distortion constant

The $\text{J =}\text{3}\text{2}\text{←}\text{1}\text{2}$ transitions of ³⁵ClO in v = 1 of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state were measured and analyzed to obtain the following constants (in megahertz: B = 18 444.86 ± 0.18, p_eff = 669.32 ± 1.08, $\text{a ? (b + c)}\text{2}\text{= 157.05 ± 0.97}$, d = 169.77 ± 0.99, and eqQ = ? 84.78 ± 0.30. The equilibrium bond length is calculated to be 1.56954 ± 0.00005 Å. The transitions in the ground vibrational state, which were reported previously, were reanalyzed by taking into account the matrix elements off diagonal in J of the hyperfine interactions, and led to a refined centrifugal distortion constant, 0.0476 ± 0.0154 MHz. The vibrational frequency increased accordingly to 782 ± 126 cm^?1, which agreed with the value 870 ± 90 cm^?1 obtained from a relative-intensity measurement, and also with other optical spectroscopic data.     

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, $\text{R′}{}_{\mathrm{e}}\text{= 3.53}\text{A}\text{?}$.     

The A′(3Π2) state of ICl

Although $\text{A′(}{}^3\text{Π}{}_2\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$ is forbidden in near case c molecules the A′ ← X transition can be efficiently accomplished by the three-step sequence $\text{A′(}{}^3\text{Π}{}_2\text{) ← D′(2) ← A(}{}^3\text{Π}{}_1\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$. Transitions to a range of levels of A′, v_A′ = 2–38, have been recorded by this means, using J-selective polarization-labeling spectroscopy. Principal constants of the A′ state of I³⁵Cl are T_e = 12682.05, ω_e = 224.57, ω_eχ_e = 1.882, ω_ey_e = ?0.0107, B_e = 0.08653, and α_e = 0.000675 cm^?1. The A′ state is therefore similar in its physical characteristics to two other (relatively) deep states, $\text{A(}{}^3\text{Π}{}_1\text{)}$ and $\text{B(}{}^3\text{Π}{}_0\text{+)}$, of the 2431 configuration.     

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.     

Diode laser spectroscopy of the SF radical

The vibration-rotation spectra of the SF radical were observed by an infrared diode laser spectrometer. The SF radical was generated directly in a cell by glow discharge in a mixture of carbonyl sulfide and carbon tetrafluoride. Zeeman modulation and discharge current modulation were employed to discriminate SF lines from many lines of the reactants and other products. Thirty two lines were assigned to the v = 1 ← 0 and 2 ← 1 bands of both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ spin states. A least-squares analysis of all the assigned lines provided precise values for molecular parameters in v = 1 and 2 and the two band origins, where ground-state constants were constrained to microwave results. The harmonic frequency ω_e was thus determined to be 837.6418(13) cm^?1, and the equilibrium bond length r_e was calculated from the B_e rotational constant to be 1.596 244(22) Å with the error in parentheses, which included 2.5 standard deviations and the uncertainty of Planck's constant.     

Measurement and interpretation of the 1-0 band of 14N16O at 1900 cm−1

The wavenumbers of the vibration rotation band lines of ¹⁴N¹⁶O are reported for the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subbands of the 1-0 transition in the infrared. The full set of spectroscopic constants for this band has been determined by direct approach using the analysis of Zare, Schmeltekopf, Harrop, and Albritton. In addition to the band origin ν₀ and the B, D, H constants for the lower and upper vibrational levels, the following spin-orbit coupling constants have been derived: $\text{A}\text{?}{}_0\text{= 123.02772 ± 0.00011}$ and $\text{A}\text{?}{}_1\text{= 122.78248 ± 0.00011}$ (in cm^?1). Apparent centrifugal corrections to these constants have been determined and the values obtained for them are $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>0</mtext>}}\text{= (0.347573 ± 0.00051) × 10}{}^{\mathrm{?3}}$ and $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>1</mtext>}}\text{= (0.337135 ± 0.00050) × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$. Λ-Type doubling constants evaluated by using both grating and tunable laser data are also reported.     

276-nm absorption band system of m-dichlorobenzene: Rotational band contour analysis

The 276-nm absorption band system (${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$) of m-dichlorobenzene was photographed under high resolution. The electronic origin band (0, 0) and a band at (0 + 380) cm^?1 were subjected to rotational “band contour” analysis. As a result, it is found that the origin band has a type A band contour and that at (0 + 380) cm^?1 exhibits a type B band contour. The band contour analysis also yields an accurate determination of the excited state parameters, viz., A′ = 0.0911 ± 0.0003, B′ = 0.02852 ± 0.00005, and C′ = 0.02175 ± 0.00001 cm^?1. A model geometry for the molecule m-DCB in its first excited singlet state has been proposed.     

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 $\text{(σ2p)}{}^2\text{(π2p)}{}^3\text{(π}{}^1\text{2p)}{}^2$.     

Pressure broadening,lineshapes, and intensity measurements in the 2 ← 0 band of NO

Lineshape and intensity measurements were made on the overtone band (v = 2 ← 0) of nitric oxide (NO) using a tunable difference-frequency laser system. Self- and N₂-pressure broadening coefficients were obtained at 296 K, and a small amount of collisional, or Dicke, narrowing (which reduces the Doppler width by ～9% at 50 Torr) was also evident. The pressure broadening observed for the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ transitions was larger than that of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ for corresponding J by about 7%, so an empirical scaling law model was fit to the broadening coefficients to determine the role of interstate (spin-flipping) collisions. A small collision-induced asymmetry in the Λ-doublet transitions of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ level was also observed. The measured line intensities yield an integrated band intensity of 1.878(_?40⁺⁹⁰) cm^?2 atm^?1 at 296 K and a Herman-Wallis F factor which determines the relative signs of terms in the dipole moment expansion.     

“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 $\text{α}{}_{\mathrm{e}}\text{(}{}^{\mathrm{o}}\text{) = 93.32}{}_8\text{± 0.02}$.     

A study of the excited electronic states of 9-fluorenone

Some spectroscopic properties of the low-energy electronic states of 9-fluorenone have been examined. The spectra in paraffin matrices at 4.2°K show detailed vibrational spectra. Two fluorescence spectra are observed; a diffuse emission arises from 9-fluorenone crystals in the paraffin matrix, and a sharp emission is characteristic of the molecule. The sharp fluorescence is analyzed in terms of known a₁ vibrational fundamentals. The sharp absorption is a near mirror-image to the fluorescence, so Herzberg-Teller vibrations are not prominent. The polarization in the crystal spectrum allows this low-energy transition near 23 000 cm^?1 to be assigned ${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$. Because there is no vibronic perturbation in fluorescence, and certainly no out-of-plane modes, a $\text{π}{}^1\text{← n}$ transition seen at about 26 000 cm^?1 is tentatively assigned ${}^1\text{B}{}_1\text{←}{}^1\text{A}{}_1$. Another sharp absorption system is seen at 31 000 cm^?1 in the paraffin matrices at 4.2°K (linewidth 6 cm^?1) but no fluorescence was detected. The polarized crystal spectrum indicated the assignment of this system and another very strong system at 40 000 cm^?1 to be ${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$, while other systems at about 34 000 cm^?1 and 44 000 cm^?1 are ${}^1\text{A}{}_1\text{←}{}^1\text{A}{}_1$.The phosphorescence spectrum of pyrene-d₁₀ held in a single crystal of 9-fluorenone at 4.2°K has been recorded. No delayed fluorescence from the host crystal is observed at 4.2°K but is intense at 77°K. The energy difference between host and guest triplet levels is estimated to be about 900 cm^?1 allowing the lowest triplet state of 9-fluorenone to be placed at 17 800 cm^?1.     

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.     

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.     

Λ-Doubling in the v = 2 ← 0 overtone band in the infrared spectrum of NO

Λ-doubling in the first overtone, v = 2 ← 0, vibration-rotation band of ¹⁴N¹⁶O has been measured with Doppler-limited resolution using a tunable difference-frequency laser spectrometer. P- and R-branch Λ-splittings for $\text{1}\text{2}\text{<- J ≤}\text{53}\text{2}$ in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ electronic state and for $\text{47}\text{2}\text{≤ J ≤}\text{57}\text{2}$ in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state have been determined by least squares fitting of the spectral profiles to Gaussian doublets with a precision of better than ±1.5 MHz for the stronger, well-resolved lines. The Λ-doubling parameters obtained from a least square Hamiltonian analysis of the data for the v = 2 level are p₂ = 349.542 (60) MHz and q₂ = 2.754 (5) MHz with the error limits representing three standard deviations. These precise v = 2 parameters are combined with excellent v = 1 constants available in the literature to calculate the Λ-splittings expected in the v = 2 ← 1 hot band of NO for comparison with recently reported measurements. The effect of nuclear hyperfine structure on the lineshapes of some of the low J overtone transitions has also been observed.     

Analysis of the Raman spectrum of SF6

The Raman active fundamentals ν₁(A1g), ν₂(Eg), ν₅(F2g), and the overtone 2ν₆ of SF₆ have been investigated with a higher resolution and the band origins were estimated to be: ν₁ = 774.53 cm^?1, ν₂ = 643.35 cm^?1, ν₅ = 523.5 cm^?1, and 2ν₆ = 693.8 cm^?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν₆ fundamental frequency is calculated as 347.0 cm^?1. From the analysis of the ν₂ Raman band, the following rotational constants of both the ground and upper states have been calculated:

$\text{B}{}_0\text{= 0.09111 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_0\text{= (0.16±0.08)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

;

$\text{B}{}_2\text{= 0.09116 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_2\text{= (0.18±0.04)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

.     

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.     

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.     

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.