W. L. Barclay

A millimeter/submillimeter spectrometer for !high resolution studies of transient molecules

A design is presented for a millimeter/submillimeter direct absorption spectrometer for studies of the pure rotational spectra of metal‐bearing free radicals. The spectrometer operates in the frequency range of 65–550 GHz with an instrumental resolution of 200–1000 kHz and an absorption sensitivity of a few ppm. The instrument utilizes phase‐locked Gunn oscillators as the tunable, coherent source of radiation from 65–140 GHz. Higher source frequencies are obtained with Schottky diode multipliers. The gas cell and optics path are designed utilizing Gaussian beam optics to achieve maximum interaction between molecules and the mm‐wave radiation in the reaction region. Scalar feedhorns and a series of PTFE lenses are used to propagate the source signal. The gas cell is a cylindrical tube 0.5 m in length with a detachable Broida‐type oven. The detector for the spectrometer is a helium‐cooled InSb hot electron bolometer. Phase‐sensitive detection is achieved by FM modulation of the Gunn oscillators and use of a lock‐in amplifier. Spectra are recorded by electrical tuning of the Gunn oscillator, which is done under computer control. The millimeter and sub‐mm rotational spectra of several free radicals have been observed for the first time using this instrument, including CaOH, MgOH, CaH, MgF, and BaOH.

The millimeter-wave spectrum of AlOH

The pure rotational spectrum of the AlOH and AlOD molecules in their X 1Sigma(+) (v = 0) ground electric states has been measured in the laboratory using direct absorption millimeter/submillimeter spectroscopy. The species were produced by the reaction of aluminum vapor, created in a Broida-type oven, with hydrogen peroxide or D2O2. Eight rotational transitions of AlOH and five transitions for AlOD were measured in the frequency range of 157-378 GHz to an accuracy better than +/- 75 kHz. Electric quadrupole interactions, arising from the aluminum nuclear spin of 5/2, were observed in the J = 4 - 5 and the J = 5 - 6 transitions of AlOH. The rotational constants of these molecules have been determined from a nonlinear least-squares fit to the data. The electric quadrupole coupling constant, eqQ, has been measured as well, and was found to have a value of -42.4 +/- 4.3 MHz. The spectra are consistent with quasi-linear ground states for AlOH and AlOD, as predicted by theory. AlOH is of astrophysical interest because of the relatively high cosmic abundance of aluminum.

The millimeter-wave spectrum of the MgOH radical (X 2Σ+)

Abstract The pure rotational spectrum of the ground electronic state (X 2 Σ + ) of the MgOH radical has been observed using millimeter/sub-millimeter direct absorption spectroscopy, as well as that of MgOD, and the less abundant magnesium isotopically-substituted species 25 MgOH and 26 MgOH. The free radicals were created in a Broida-type oven by the reaction of metal vapor with hydrogen peroxide. The spin—rotation splitting was readily observed in these data; however, the hyperfine structure was only resolved for 25 MgOH. The rotational and spin—rotation constants of the radicals have been determined from a non-linear least-squares fit using a 2 Σ Hamiltonian. The 25 Mg hyperfine constants are also estimated.

Millimeter‐wave spectroscopy of vibrationally excited ground state alkaline‐earth hydroxide radicals (X 2Σ+)

Pure rotational spectra of the alkaline‐earth monohydroxides have been recorded for vibrationally excited states (0 1 0), (0 2 0), (0 3 0), and (1 0 0) of the ground electronic state (X 2Σ+) using millimeter‐wave absorption spectroscopy. The radicals MgOH, CaOH, SrOH, and BaOH were studied. The data for CaOH, SrOH, and BaOH were analyzed with a linear 2Σ+ model, but with the addition of two terms to account for contamination of the v2=1 2Π and v2=2 2Δ vibronic levels with 2Π and 2Δ electronic states. The data for MgOH, however, did not fit well to this linear model and is additional evidence that this species is quasilinear.

The millimeter-wave spectrum of the SrOH and SrOD radicals

Abstract The pure rotational spectra of the X 2 Σ + ground states of the SrOH and SrOD radicals have been observed in the laboratory using millimeter/submillimeter direct absorption spectroscopy. The lesser abundant isotopically substituted species, 86 SrOH, has been observed as well. The molecules were produced in a Broida-type oven by the reaction of Sr metal vapor with either H 2 O 2 or D 2 O 2 . The rotational and spin—rotation constants were determined for the radicals from a nonlinear least-squares fit to the data using a 2 Σ Hamiltonian. The millimeter-wave measurements support the picture that strontium hydroxide is linear in its ground electronic and vibrational state.

NEW ROVIBRATIONAL DATA FOR MgOH AND MgOD, AND THE INTERNUCLEAR POTENTIAL FUNCTION OF THE GROUND ELECTRONIC STATE

Abstract Using millimeter wave absorption spectroscopy we have recorded pure rotation spectra of MgOH in its ground vibrational state and in six excited vibrational states. We have also determined a large number of bending vibrational energies, and the MgO stretching frequency, using dispersed fluorescence studies of both MgOH and MgOD. By a weighted least-squares optimized fitting to this data, using the vibrational approach MORBID (Morse oscillator rigid bender for internal dynamics), we have derived the full ground state potential surface in an analytical form. The equilibrium structure is determined to be linear but with a flat predominantly quartic bending potential.

The millimeter-wave spectrum of the MgH and MgD radicals

The pure rotational spectrum of MgH radical (X 2 Sigma (+)) in its ground state v = 0 and v = 1 vibrational modes has been observed in the laboratory using millimeter/submillimeter direct absorption spectroscopy. The rotational spectra of two isotopically substituted species, MgD and (Mg-26)H, have been detected as well. All six hyperfine components of the N = 0 -1 transition of MgH in its v = 0 and v = 1 states have been directly measured to an accuracy of +/-50 kHz, and the five components have been observed for (Mg-26)H. The N = 0 +/-1 and N = 1 -2 transitions of MgD have also been detected. Rotational, fine structure, and hyperfine constants were determined for all species from a nonlinear least-squared fit to the data using a 2 Sigma Hamiltonian.

The millimeter-wave spectrum of CaH (X 2Sigma(+))

The millimeter-wave spectrum of the CaH and CaD radicals (X 2Sigma(+)) has been observed in the laboratory via direct absorption spectroscopy. The species were generated by the reaction of calcium vapor, produced in a Broida-type oven, with hydrogen atoms created in a microwave discharge. The six hyperfine components of the N = 0 yields 1 rotational transition of CaH near 254 GHz were resolved and their frequencies determined to an accuracy of +/- 100 kHz. The main hyperfine lines originating in the N = 0 yields 1, 1 yields 2, and 2 yields 3 rotational transitions of CaD were also detected. Spectroscopic constants were determined for both radicals from a nonlinear least squares fit to the data, using a 2Sigma Hamiltonian. These measurements constitute the first laboratory observation of CaH at high spectral resolution, and are essential to the detection of this radical in interstellar space.

A molecular beam millimeter-wave optical pump/probe study of the X 1Σ+ state of yttrium monofluoride

Abstract The J =4-3, J =5-4, and J =6-5 pure rotational transitions in the ground X 1 Σ + state of yttrium monofluoride, YF, have been recorded by molecular beam millimeter-wave optical pump/probe spectroscopy. This study demonstrates that high resolution ( B =8683.65 (1) MHz, and D =0.0079 (2) MHz.

The laboratory spectrum of acetaldehyde at 1 millimeter (230-325 GHz)

The rotational spectrum of acetaldehyde (CH3CHO) in the frequency range 230-325 GHz has been measured in the laboratory using millimeter/submillimeter direct absorption spectroscopy. Over 250 transition frequencies are presented for this molecule for both A and E symmetry species in its ground (upsilon(sub t) = 0) and first excited (upsilon(sub t) = 1) torsional state, with experimental uncertainties of +/- 50 kHz. The data were fitted with a model involving an internal rotation potential function, which typically reproduces the measured frequencies to nu(sub obs) - nu(sub calc) less than or approximately 50 kHz for both ground and upsilon(sub t) = 1 state. These newly measured rest frequencies should aid in the identification of interstellar CH3CHO and in spectral line assignments for millimeter-band scans.