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:

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

;

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

.     

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°.     

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

Rotation-vibration analysis of the Coriolis-coupled ν5g, ν6g, ν8g and ν9 bands of H2CCO

Medium resolution infrared grating spectra of gaseous ketene, H₂CCO were recorded between 1000 and 400 cm^?1, both at instrument temperature (40°C) and with cooling (?40°C). Interferometric Fourier spectra were also measured at ?70°C with resolution 0.22 cm^?1 between 450 and 330 cm^?1. The K structure of the fundamentals ν₅, ν₆, ν₈, and ν₉ was assigned. These fundamentals are coupled by a-axis Coriolis interactions. These couplings were analysed on the symmetric top basis for setting up the perturbation matrix and by utilizing the K-dependent Coriolis shifts of levels. A preliminary analysis of the Coriolis intensity anomalies was also undertaken.Band center values from combination differences are $\text{ν}{}_5{}^0\text{= 587.30 (27)}$ and $\text{ν}{}_6{}^0\text{= 528.36 (39)}\text{cm}{}^{\mathrm{?1}}$. Synthetic spectra indicate the band origins of ν₈ and ν₉ to be close to 977.8 and 439.0 cm^?1, respectively. Estimates of Coriolis coupling constants obtained from synthetic spectra are $\text{ζ}{}_{58}{}^{\mathrm{a}}\text{= + 0.33 (5)}$, $\text{ζ}{}_{68}{}^{\mathrm{a}}\text{= + 0.714 (20)}$, $\text{ζ}{}_{59}{}^{\mathrm{a}}\text{= ? 0.774 (20)}$, and $\text{ζ}{}_{69}{}^{\mathrm{a}}\text{= ? 0.30 (2)}$. Approximate ratios of unperturbed vibrational transition moments obtained from spectral simulations are $\text{M}{}_8{}^0\text{:±iM}{}_5{}^0\text{:±iM}{}_6{}^0\text{:M}{}_9{}^0\text{≈ +2:?9:+10:+0.5}$.     

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.     

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 $\text{Br}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_2\text{) +}\text{Br}{}^{\mathrm{?}}\text{(}{}^1\text{S}{}_0\text{)}\text{is 34 700 cm}{}^{\mathrm{?1}}$.     

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

Intensity measurements,self-broadening coefficients,and rotational intensity distribution for lines of the oxygen B band at 6880 Å

Quantitative measurements of intensities and half-widths were made for individual rotational lines of the atmospheric oxygen B band. The total band intensity, as derived from the line intensity measurements, is 40·8±0·6 cm^?1km^?1atm^?1 STP. As had been previously found in this laboratory for the oxygen A band, the relative line intensities conform closely to the rotational distribution calculated by either Schlapp or by Watson. The line half-widths at half-intensity were determined for oxygen self-broadening for the ${}^{\mathrm{P}}\text{Q}$ and ${}^{\mathrm{P}}\text{P}$ branch lines and for a few ${}^{\mathrm{R}}\text{Q}$ and ${}^{\mathrm{R}}\text{R}$ branch lines near the band origin, and were found to vary from 0·064 cm^?1atm^?1 at J′ = 1 to 0·042 cm^?1atm^?1 at J′ = 25.     

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.     

Band contour analysis of compounds with pure isotopes: The E fundamentals of HC35Cl3

The vibration-rotation transitions for v = 1 ← 0 of NO (${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) have been studied by using the technique of laser magnetic resonance spectroscopy. Five magnetic resonance lines are observed with three CO laser lines in the range from 1859 to 1886 cm^?1. From these, three zero-field transition frequencies, v = 1 ← 0; $\text{R(}\text{3}\text{2}\text{)}$, $\text{P(}\text{7}\text{2}\text{)}$, and $\text{P(}\text{9}\text{2}\text{)}$ are obtained with an accuracy of ±0.0007 cm^?1. The molecular constants which have been determined by borrowing centrifugal constants from a previous infrared work are $\text{B}{}_{02}{}^1\text{= 1.72004 ± 0.00006}\text{cm}{}^{\mathrm{?1}}$, $\text{B}{}_{12}{}^1\text{= 1.70212 ± 0.00010}\text{cm}{}^{\mathrm{?1}}$, and $\text{G(v = 1) ? G(v = 0) (}\text{for}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{) = 1875.8470 ± 0.0007}\text{cm}{}^{\mathrm{?1}}$.     

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.     

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.     

Remeasurement of the low-energy cross section for the 15N(p, α0)12C reaction

The cross section for the ${}^{15}\text{N(p}\text{, α}{}_0\text{)}{}^{12}\text{C}$ reaction has been measured at θ_lab = 135° over the proton energy range 93 ≦ E_p ≦ 418 keV. The results are in good agreement with the less precise but much earlier measurements of Schardt, Fowler and Lauritsen (1952). An analysis of the present data in terms of a two-level calculation including the 338 keV (1^?) and 1028 keV (1^?) resonances determines a zero-energy intercept for the astrophysical S-factor of S(0) = 78 ± 6 MeV · b.     

Charmed baryon pair production in e+e− annihilation

Cross sections for charmed baryon pair production near threshold in e⁺e^? annihilation are calculated using pole-dominated form factors modified to take intoccount continuum effects. When the C₀⁺$\text{C}$₀^? production cross section is normalized with the help of data for $\text{e}{}^{\mathrm{+}}\text{e}{}^{\mathrm{?}}\text{→}\text{p}\text{X}$ it is found that the total charmed baryon production cross $\text{(}\text{C}{}_0\text{C}{}_0\text{,}\text{C}{}_1\text{C}{}_1\text{,}\text{C}{}_1\text{C}{}_1{}^1\text{+}\text{C}{}_1{}^1\text{C}{}_1\text{,}\text{C}{}_1{}^1\text{C}{}_1{}^1\text{)}$ reaches a peak value of approximately 2.7 nb at √s = 5 GeV.     

The infrared part of the C2 Phillips system (2.3–0.9 μm)

Line positions and molecular constants for the 0-0, 1-0, 2-0, 0-1, 2-1, 3-1, 0-2, 1-2, and 4-2 bands of the C₂ Phillips system ($\text{A}{}^1\text{Π}{}_{\mathrm{u}}\text{-X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$) are reported. Among them, five bands have not been reported previously. Rotational perturbations have been observed in the previously unobserved v = 1 level of the $\text{A}{}^1\text{Π}{}_{\mathrm{u}}$ state. This state is perturbed by the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state which was discovered by Ballik and Ramsay. These observations provide new information regarding the perturbing state. In particular, the minimum of the potential energy for the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state has been found to be at 9227.4 cm^?1 instead of 13 310 cm^?1, which was the previous T_e value for this electronic state.     

Optical absorption spectrum of hematite, αFe2O3 near IR to UV

Optical absorption spectra have been measured on thin (011) single crystal platelets and on highly oriented (110) thin films of αFe₂O₃. We have observed and assigned some of the absorption bands predicted by ligand field theory and SCF-Xα calculations. The temperature dependence of the 11760 cm^?1 single crystal band has been fitted to the function $\text{? = ?}{}_0\text{(1 + exp (?}\text{θ}\text{T}\text{))}$ with $\text{?}{}_0\text{= 0.85 × 10}{}^{\mathrm{?4}}$ and θ = 200 K (139 cm^?1). We have measured the photocurrent as a function of wavelength and have found several peaks that coincide with optical absorption bands.     

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.     

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.     

Energy levels of low lying triplet states of N2 from infrared emission studies

A theoretical model used to describe the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states of N₂ is presented. Using recently acquired high resolution spectra of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ (0-0) band, rotational energy levels of the v = 0 vibrational levels of these two states are generated with this model. These levels are in excellent agreement with those obtained using a combination differences technique. The precision of the model generated levels is 0.01 cm^?1. The previously unpublished rotational levels of Dieke and Heath for the $\text{A}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, B³Π_g and C³Π_u states are referenced to the $\text{N}{}_2\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ (v = 0, J = 0) ground level and tabulated here. Estimates of the precision of their work are made.     

The 2780 Å absorption system of thiophosgene

The vapor phase absorption spectrum of thiophosgene (Cl₂CS) in the 2500–2900 Å region consists of a broad intense band ($\text{log}\text{?}{}_{\mathrm{<mtext>max</mtext>}}\text{= 3.5}\text{at}\text{2540}\text{A}\text{?}$. On the red side of this a vibrationally discrete structure is found which becomes increasingly diffuse and merges into the broad band as the wavelength is decreased. It is shown that this vibrational structure can be explained as due to a $\text{π → π}{}^1$, ${}^1\text{A}{}_1\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ electronic transition between a planar ground state and a pyramidal excited state of the molecule. In the latter state, the CS stretching mode ν₁′(a₁) = 681 cm^?1 and the CCl bending mode ν₃′(a₁) = 147 cm^?1. From the inversion doublet splitting of the out-of-plane mode ν₄′(b₁), the barrier to inversion is calculated to be ～126 cm^?1, with an equilibrium out-of-plane angle of ～20°.