Engineering topics
Publications and source records attributed to De Lucia, Frank C..
Ethyl alcohol (ethanol) is known to possess a pair of closely-spaced excited torsional substates (gauche +, gauche -) at an energy of approximately 57 K above the ground (trans) torsional substrate. We report an extended analysis of some gauch- - gauch+ Q branch (delta J=0) transitions witha three-substrate fixed frame axis method (FFAM) Hamilton.
The high-resolution laboratory millimeter- and submillimeter-wave spectra of C-12H(3)OH and C-13H(3)OH have been extended to include transitions involving significantly higher angular momentum quantum numbers than studied previously. For C-12H(3)OH, the data set now includes 549 A torsional substate transitions and 524 E torsional substate transitions through J is not greater than 24, exclusive of blends. For C-13H(3)OH the data set now includes 453 A torsional substate transitions and 440 E torsional substate transitions through J is not greater than 24, exclusive of blends. The extended internal axis method Hamiltonian has been used to analyze the transitions to experimental accuracy. The molecular constants determined by this approach have been used to predict accurately the frequencies of many transitions through J = 25 not measured in the laboratory.
To facilitate studies of water in the interstellar medium and late-type stars, the frequencies of 30 new millimeter- and submillimeter-wave transitions of H2O-16 have been measured, which lie between 100 GHz and 600 GHz. This represents almost a doubling of the number of water lines that have been observed in the laboratory in this spectral region at high resolution. All of the newly observed lines are highly excited, lying between 2400 and 4200/cm above the ground level. Some of these have large excitation energies because of their high rotational states and others because they lie in excited vibrational states. These lines are potentially of substantial astrophysical significance because they are related to the study of interstellar masers and because their high excitation eliminates the atmospheric self-absorption associated with the more well-known water lines.
A total of 245 previously unobserved millimeter- and submillimeter-wave transitions of (C-13)H3OH for J not above 10 were assigned on the basis of measurements with a spectrometer which uses 40-60 GHz klystrons as fundamental radiation sources. These transitions were combined with the previously assigned 596 transitions and were analyzed using a modified internal-axis-method model which treats the symmetric (A) and degenerate (E) substates separately. As a result of the expansion of the (C-13)H3OH data set to cover the same range as the data set of a previous (C-12)H3OH analysis by Anderson et al. (1990), rigid criteria of self-consistency could be applied for the selection and the value of the constants between the isotopic species. The spectral constants obtained were used to make accurate predictions of 562 additional transitions of (C-13)H3OH for v(t) = 0, 1, 2 and rotational quantum number J equal to or less than 12.
Pressure-broadening parameters for 19 transitions of the millimeter and submillimeter wave spectrum of NO2 have been obtained experimentally. Results for broadening by N2, O2, and He are presented and compared with earlier theoretical calculations of the N2 and O2 parameters. A discussion of the relation between theoretical calculations and experimental measurements is presented.
In order to aid in the interstellar identification of molecular oxygen via its (O-16)(O-18) isotopic species, the frequencies of four rotational fine-structure lines of (O-16)(O-18) have been measured at frequencies ranging from 298 to 464 GHz. The line with the highest intensity and consequent best chance of astronomical detection lies at 401739.823 MHz. Its magnetic dipole strength is somewhat more than half that of the previously measured strong line at 233946.179 MHz.
The rotational-torsional spectrum of (C-13)H3OH is presented in both the symmetric and degenerate substates of the first two excited torsional states. Of the new transitions reported, 122 lines are from the v(t) = 1 torsional state and 110 lines are from the v(t) = 2 torsional state, and all are confined to the rotational quantum number J = 8 or less. The data are combined with previously reported millimeter and submillimeter data for the v(t) = 0 torsional state and 44 previously measured excited torsional state lines to form a global data set of 596 transitions, which is analyzed and fitted using an extended internal axis method. The fit results in an overall rms deviation of 1.98 MHz. The spectral constants generated by the fit are used to predict an additional 123 lines of (C-13)H3OH in the v(t) = 1,2 excited torsional states with frequencies up to 612 GHz and rotational quantum number J = 11 or less.
The pressure-broadening coefficients of four molecules of atmospheric significance (NO2, CF2Cl2, HDO and HOOH) have been measured in the millimeter wave region. For each species, two transitions near 230 GHz were broadened by both N2 and O2, for a total of 16 different pressure-broadening measurements. Intercomparisons among the results of these measurements, as well as recent more extensive measurements on HNO3, are considered.
The details of work on the nu(8) vibrational state, which arise from the NO2 out-of-plane vibration, are reported. For this state, over 210 transitions have been measured in the millimeter and submillimeter spectral region and analyzed with Watson's A-reduced centrifugal distortion Hamiltonian. Also included in this work is a comparison of all these spectra and an overview of the millimeter and submillimeter spectra associated with these states. Although at the high sensitivity available in laboratory experiments, many additional lines are observable, all arise from vibrational states whose populations are more than 100 times lower than the ground state. The most prominent of these are due to the states which give rise to the perturbed 2 nu(9) and nu(5) bands near 11 microns. These results provide a significant data base for both atmospheric remote sensing experiments and spectral analyses of data in other spectral regions, especially the IR.
The millimeter-wave and submillimeter-wave spectrum of CH3OD, a deuterated isotope of methanol known to be present in the interstellar medium, has been studied in the laboratory. Like all isotopes of methanol, CH3OD possesses a complex dense spectrum because of the phenomenon of internal rotation, sometimes referred to as torsional motion. Approximately 300 lines in the frequency range 130-700 GHz have been assigned. These lines involve transitions between rotational states with rotational quantum number J of not greater than 9 in both the A and the E substates of the lowest torsional state (v sub t = 0). The present data and previous data at lower frequencies (longer wavelengths) have been combined and analyzed by a procedure called the 'internal axis method'. The analysis yields spectral constants for CH3OD which, in turn, have been used to predict the frequencies of a number of other transitions of this species not measured in the laboratory.
A comprehensive millimeter- and submillimeter-wave study of the rotational spectrum of (C-13)H3OH is presented. Approximately 300 new transitions of this species were measured at frequencies up to 650 GHz, and the transitions were analyzed along with previously measured spectra using the internal axis method of Herbst et al. (1984). The resulting spectral constants allow prediction of an additional large number of transitions which should allow astronomers to identify many strong rotational lines of C-13 methanol throughout much of the submillimeter region.
Based on previously determined spectral constants for methyl formate in its ground torsional degenerate substate, the frequencies and intensities of forbidden c-type transitions in this molecule, which is represented by a large number of lines in OMC-1, are calculated along with other 'forbidden' transitions labeled x-type. The stronger c-type transitions below 300 GHz with angular momentum quantum number of 30 or less and with upper state rotational energy of 350/cm or less are included in a list of spectral frequencies presented in this paper. Because the c-type transitions borrow intensity from the b-type transitions, the intensities of strongly affected b-type spectra are recalculated and presented.