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.     

Microwave spectroscopy of the CCl radical

The CCl radical was generated by a dc glow discharge in CCl₄, and rotational transitions of C³⁵Cl in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ were observed in the mm-wave region by using a source modulation microwave spectrometer. From an analysis of the observed spectra the magnetic and electric quadrupole hyperfine coupling constants of the ³⁵Cl nucleus were determined precisely. The Λ-doubling constant p₀ was determined to be positive, indicating that unknown ²Σ^? excited electronic states are making dominant contributions to the Λ doubling in the ground state. The previous diode-laser result [J. Mol. Spectrosc.85, 416–426 (1981)] was reanalyzed by using improved wavelength standards and by fixing the ground-state parameters to the present microwave values including the B₀ rotational constant 20 797.1725(38) MHz. The vibration-rotation constant α^B and the equilibrium bond length r_e were thus determined to be 0.006 768 2(48) cm^?1 and 1.645 218(16) Å, respectively, with 2.5 times standard deviations in parentheses. The spin density on the chlorine atom was estimated to be about 0.20 from the observed hyperfine coupling constants.     

Diode laser spectroscopy of ammonia overtone transitions

Summary Diode laser spectroscopy of ammonia ro-vibrational overtone transitions has been performed in the near IR, by using direct absorption, wavelength modulation, and two-tone frequency modulation techniques. Pressure broadening coefficients in air, hydrogen, helium and self-broadening have been measured. The high sensitivity of the apparatus permitted the detection of 70 p.p.m. of NH₃ in air per meter of path at atmospheric pressure. New lines have been observed in the 719.9 nm band. The authors of this paper have agreed to not receive the proofs for correction.     

Diode laser spectroscopy of overtone bands of acetylene

Overtone absorption lines of acetylene in the regions around 12700 and 11800 cm^–1 have been examined by the use of tunable diode lasers in free-running mode. The diode laser emission wavelength was scanned around the gas resonances by simply sweeping its injection current, permitting a direct observation of the absorption line-shapes. Weak overtone absorption lines have been detected by using the wavelength modulation (WM) spectroscopy with 2nd harmonic detection technique and the collisional broadening and shift coefficients have been obtained. The high resolving power and accuracy of the spectrometer permitted a wavenumber error of less than 0.01 cm^–1. The correct interpretation of the absorption signals when detecting the second harmonic in the presence of a sloping background is discussed.     

Diode laser spectroscopy of several bands of hydroxylamine

Diode laser spectroscopy has been carried out on the ν₅ (1115 cm⁻¹) and ν₆ (895 cm⁻¹) fundamentals, the 2ν₉ overtone, the 3ν₉-ν₉ hot band, and the ν₅-ν₉ difference band (all near 700 cm⁻¹) of hydroxylamine (NH₂OH). (ν₅ = NH₂ wag, ν₆ = NO stretch, and ν₉ = OH torsion.) Transition frequencies were determined with a nominal accuracy of ±0.001 cm⁻¹. Accurate molecular parameters were determined for the ground state, v₆ = 1, v₉ = 1, and v₉ = 2. The v₅ = 1 and v₉ = 3 states were perturbed by a Coriolis interaction with each other and possibly with a third state. In these cases effective rotational and distortion constants were determined together with empirical perturbation parameters. The data obtained on ν₅ and ν₆ enabled assignments of the transitions involved in the optically pumped hydroxylamine FIR laser to be made.     

Diode laser spectroscopy: Water vapour detection in the atmosphere

Summary Diode laser spectroscopy of water vapour has been performed in the near IR and the pressure broadening coefficients in nitrogen and in air have been measured for one rotovibrational line. Detection of water vapour in the atmosphere has been obtained and an evaluation of the sensitivity of our apparatus is reported. Discussion for further improvements is made.     

Diode laser spectrometer for high-resolution spectroscopy in the visible range

A high-resolution diode laser spectrometer operating at 657 nm is described. To achieve a narrow linewidth and a high power, a master-slave laser system is employed. The master laser is an extended cavity diode laser whose linewidth is reduced to less than 100 Hz by the FM sideband technique. The slave laser is an AR-coated diode laser and characteristics of injection locking are experimentally studied. The injection current of the slave laser is utilized to stabilize the output power or to produce pulsed output. Using this spectrometer, we probed the intercombination line of Ca and observed high-contrast optical Ramsey fringes with a linewidth of 10 kHz. A velocity-selective Ramsey fringe is also observed in the pulse-mode operation.     

Infrared diode laser spectroscopy of the BrO radical

The fundamental vibration-rotation band of the ⁷⁹BrO and ⁸¹BrO radicals in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ ground electronic state was observed in the region 700–760 cm^?1 by using a Zeeman-modulated infrared diode laser spectrometer. The BrO radical was generated directly in a multiple reflection Zeeman cell by a 60-Hz discharge in a mixture of Br₂ and O₂. The observed absorption lines, 20 and 22 in number for ⁷⁹BrO and ⁸¹BrO, rspectively, were combined with the microwave data of Cohen et al. [J. Mol. Spectrosc.87, 459–470 (1981)] and were subjected to least-squares analysis to determine the rotational and centrifugal distortion constants for both the v = 0 and v = 1 states and also the band origin. The band origin obtained for ⁸¹BrO, 721.92814(57) cm^?1, gives a support to the value 714 (10) cm^?1 estimated by Cohen et al. using the microwave data and also the result 722.1 ± 1.1 cm^?1 obtained by Barnett et al. [Canad. J. Phys.59, 1908–1916 (1981)] from a reanalysis of the A²Π_i-X²Π_i absorption spectrum.     

Infrared diode laser spectroscopy of the PO radical

Vibration-rotation transitions of the PO radical in the X²Π_r state have been observed by a tunable infrared diode laser spectrometer. The analysis of the observed spectra gave the molecular constants in the v = 1 state and the band origin to be B = 0.7250107(36), D = 1.0253(60) × 10^?4, A_J = 0.997(24) × 10^?4, p = 0.006323(33), A₁ - A₀ = 0.16354(78), and ν₀ = 1220.24901(43), all in cm^?1 units with three standard errors in parentheses, where the v = 0 parameters were fixed to the values previously reported. The equilibrium internuclear distance was determined to be $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 1.476370(15)}\text{A}\text{?}$.     

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.     

Near-infrared diode laser spectroscopy of the HCSi radical

The , , and band spectra of HCSi radical were investigated by means of near-infrared diode laser spectroscopy to determine precise molecular constants for the and states. The detailed analysis of the rotationally resolved band spectra, studied for the first time in the present investigation, leads to the precise determination of molecular constants for the state associated with the Renner-Teller interaction. We obtained −0.15126663(53) and 495.00698(30) cm⁻¹ as the Renner-Teller parameter ε and the bending vibrational frequency ω₂, respectively. Based on the molecular constants for the and states, the rotational levels of the state were analyzed to obtain molecular constants and information on upper state perturbations. Using the available spectroscopic data, valence force fields for both the and states were estimated to aid in understanding the vibrational energy levels of the HCSi radical.     

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.     

Doppler-limited dye laser excitation spectroscopy of the HSO radical

The cw dye laser excitation spectrum of the vibronic transition of the HSO radical was observed between 16 420 and 16 520 cm⁻¹ with Doppler-limited resolution, 0.03 cm⁻¹. The HSO radical was produced by reaction of discharged oxygen with H₂S or CH₃SH. The observed spectra were assigned to 751 transitions of the K′_a ← K″_a = 2 ← 3, 1 ← 2, 0 ← 1, 1 ← 0, 2 ← 1, and 3 ← 2 subbands, and were analyzed to determine rotational constants, centrifugal distortion constants, and spin-rotation interaction constants with good precision. The signs of the spin-rotation interaction constants were determined for both the upper and the lower state from the observed spectra. The band origin obtained is 16 483.0252 (2.5σ = 0.0013) cm⁻¹. The molecular constants which were determined reproduce the observed transitions with an average deviation of 0.0045 cm⁻¹.     

Doppler-limited dye laser excitation spectroscopy of the CCN radical

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^2\text{Δ}\text{(000) ←}\text{X}\text{?}{}^2\text{Π}\text{(000)}$ vibronic transition of the CCN radical was observed between 21 205 and 21 335 cm^?1 with the Doppler-limited resolution, 0.04 cm^?1. The CCN radical was produced by reaction of microwave discharged CF₄ with CH₃CN. The observed spectrum was analyzed to determine rotational and centrifugal constants and effective spin-orbit and spin-rotation coupling constants for both the $\text{A}\text{?}{}^2\text{Δ}\text{(000)}$ and the $\text{X}\text{?}{}^2\text{Π}\text{(000)}$ states, and also the Λ-type doubling constants for the $\text{X}\text{?}{}^2\text{Π}\text{(000)}$ state. The constants determined reproduce the observed spectrum with an average deviation of 0.0027 cm^?1, and are considered to be precise enough for predicting the ground-state microwave transition frequencies. No evidence was found for perturbation in either the $\text{A}\text{?}{}^2\text{Δ}\text{(000)}$ or the $\text{X}\text{?}{}^2\text{Π}\text{(000)}$ state.     

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.     

Diode laser absorption spectroscopy for studies of gas exchange in fruits

Gas exchange in fruits, in particular oxygen transport in apples, was studied non-intrusively using wavelength modulation diode laser absorption spectroscopy at about 761 nm, applied to the strongly scattering intact fruit structure. The applicability of the technique was demonstrated by studies of the influence of the skin to regulate the internal oxygen balance and of cling film in modifying it by observing the response of the signal from the internal oxygen gas to a transient change in the ambient gas concentration.Applications within controlled atmosphere fruit storage and modified atmosphere packaging are discussed. The results suggest that the technique could be applied to studies of a large number of problems concerning gas exchange in foods and in food packaging.     

Diode laser spectroscopy of ammonia at 760 nm

A tunable diode laser spectrometer has been employed to examine the unknown overtone absorption lines of NH₃ around (760 nm). The spectrometer sources are commercially available heterostructure AlGaAs tunable diode lasers operating in the “free-running” mode. The detection of the lines has been possible by the use of the wavelength modulation spectroscopy and the second harmonic detection technique. A special algorithm has been used in order to fit the highly modulated absorption lines. The weakest observed resonances have absorption cross sections on the order of ?/molecule or ?/amagat. For some of the more intense lines self-, air-, N₂-, He- and H₂-broadening coefficients have been obtained at room temperature and also some shifting coefficients have been measured.     

Diode laser spectroscopy of ethylene overtones at 830 nm

A tunable diode laser spectrometer has been employed to examine the 3rd overtone absorption lines of C₂H₄ at around 12 000 cm⁻¹ (830 nm). The spectrometer sources are heterostructure AlGaAs tunable diode lasers operating “free-running”. By the aid of the wavelength modulation spectroscopy with the second harmonic detection technique and a Herriott type multipass cell 63 very weak absorption lines have been observed for the first time, with cross sections as low as 2 × 10⁻²⁶ cm²/mol, equivalent to . The self-broadening coefficient has been measured for one of the most intense lines.     

Diode laser spectroscopy using two modes of an InAsSb/InAsSbP laser near 3.6 μm

A new type of multimode semiconductor laser, based on InAsSb/InAsSbP heterostructures, is described. This continuous laser working in a broad range of temperatures (30–100 K) was tested using a closed-cycle He-cryostat and its quality was demonstrated using the laser spectroscopy of gases absorbing in the 2800 cm^-1 region. Two different laser modes were used to increase the spectral range. The spectral characteristics and tunability of the laser were explored as a function of heat-sink temperature and drive current with the aim of developing its use for high–resolution spectroscopy. The laser has potential applications in the field of chemistry, atmospheric research and the study of the kinetics of reactive species. Received: 18 October 1999 / Revised version: 10 May 2000 / Published online: 16 August 2000