Engineering topics
Publications and source records attributed to Herbst, Eric.
We discuss past and recent progress in our long-term laboratory program concerning the submillimeter-wave rotational spectroscopy of known and likely interstellar molecules, especially those associated with regions of high-mass star formation. Our program on the use of spectroscopy to study rotationally inelastic collisions of interstellar interest is also briefly mentioned.
Currently, millimeter-wave and submillimeter-wave spectroscopy is conducted in our laboratory on several different types of spectrometers. Our standard spectrometer utilizes the output of a phase-locked klystron operating in the 40-60 GHz region, which is sent into a crossed-waveguide harmonic generator, or "multiplier". The high frequency millimeter-and submillimeter-wave radiation is transmitted via quasi-optical techniques through an absorption cell and then onto a detector, which is either an InSb hot electron bolometer cooled to 1.4 K or a Si bolometer cooled to 0.3 K. The detector response is sent to a computer for measurement and analysis. The frequency range produced and detected in this manner goes from 80 GHz to upwards of 1 THz. Spectra are normally taken with source modulation, with line frequencies typically measured to an accuracy of 50-100 kHz. Higher accuracy is available when needed. Recently, we developed a new, broad-band spectrometer in our laboratory based on a free-running backward wave oscillator (BWO) of Russian manufacture as the primary source of radiation. The so-called FASSST (fast-scan submillimeter spectroscopic technique) system uses fast-scan and optical calibration methods rather than the traditional locking techniques. The output power from the BWO is split such that 90% goes into the absorption cell while 10% is coupled to a 40-meter Fabry-Perot cavity, which yields fringe? for frequency measurement. Results from this spectrometer on the spectrum of nitric acid (HNO3) show that 100 GHz of spectral data can be obtained in 5 seconds with a measurement accuracy of 50 kHz. Currently, the frequency range of the FASSST system in our laboratory is roughly 100-700 GHz.
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 substate. We report an extended analysis of some gauche - gauche+ Q-branch ((Delta)J = 0) transitions with a three-substate fixed frame axis method (FFAM) Hamiltonian. Our approach accounts for complex trans-gauche interactions for the first time. In addition, we are able to obtain intensities for perturbed rotational transitions, and to determine the trans to gauche+ separation to be 1185399.1 MHz. A complete ground state rotational-torsional partition function accounting for the previously neglected gauche substates is presented. Based on our analysis, a total of 14 U lines obtained towards Orion KL can now be assigned to gauche substates of ethanol. Analysis of these lines yields a rotational temperature of 223 K and a total (trans + gauche) column density of 7.0 x 10(exp 15)/sq cm. The column density is in reasonable agreement with the recent value of 2-3 x 10(exp 15)/sq cm based on observations of trans-ethanol by Ohishi et al., although there is some disparity in the rotational temperatures. Eight additional U lines in the literature are assigned to transitions of gauche ethanol.
We report an investigation of the rotational-torsional spectrum of the gauche rotational isomers of ethyl alcohol in the 51-505 GHz frequency region. Over a thousand transitions between rotational levels in the gauche substates of the ground OH torsional state have been measured and assigned. These transitions involve rotational quantum numbers J and K(sub a) up to 30 and 15, respectively, and are of two types: alpha-type transitions between levels in either the gauche+ or the gauche-substate, and c-type transitions between rotational levels in the different substates. The majority of these transitions have been fit satisfactorily using a two-state Hamiltonian based on the Fixed Framework Axis Method (FFAM). The rotation, distortion, and interaction constants have been determined along with the energy difference between the two gauche substates. The derived constants can be used to predict many more transitions accurately for astronomical purposes. The J and K(sub a) region where the two-state analysis can be used has been determined. The basis for a three-state analysis including the trans substate is presented and the applicability of the FFAM approach is discussed.
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.
We report an investigation of the rotational-torsional spectrum of the gauche rotational isomers of ethyl alcohol in the 51е05 GHz frequency region. Over a thousand transitions between rotational levels in the gauche substates of the ground OH torsional state have been measured and assigned. These transitions involve rotational quantum numbers J and Ka up to 30 and 15, respectively, and are of two types: a-type transitions between levels in either the gauche+ or the gaucheРsubstate, and c-type transitions between rotational levels in the different substates. The majority of these transitions have been fit satisfactorily using a two-state Hamiltonian based on the fixed framework axis method (FFAM). The rotation, distortion, and interaction constants have been determined along with the energy difference between the two gauche substates. The derived constants can be used to predict many more transitions accurately for astronomical purposes. The J and Ka region where the two-state analysis can be used has been determined. The basis for a three-state analysis including the trans substate is presented and the applicability of the FFAM approach is discussed.!
The laboratory millimeter-wave and submillimeter-wave rotational spectrum of propionitrile (ethyl cyanide, C2H5CN) in its ground vibrational state has been extended through J = 70 and K(sub a) = 36. Transitions measured in this study are in the frequency range 250-610 GHz. A fit of 952 transitions including 732 new measurements to a Watson A-reduced Hamiltonian has yielded a complete set of quartic and sextic distortion constants, in addition to six octic distortion constants. Internal rotation and hyperfine splittings have not been resolved, so they are not included in the analysis. Predicted transition frequencies for a large number of additional transitions of interest to radioastronomers are provided.
The ab initio results presently obtained for the potential energy surface of competing associative and reactive ion-molecule processes of the reactants H2 and C3H(+) show that the linear ion is able to directly access the deep potential well of the propargyl ion H2CCCH(+). Using the minimum energy potential pathway and properties of the stationary point structures determined via the ab initio methods, calculation results are obtained for both the association-rate coefficient for C3H3(+) production as a function of density, and the branching ratio between the propargyl and cyclic structures of the ion.
Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.
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.
The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.
The ion-molecule reaction of C + H3(+) - CH(+) + H2 has not been studied in the laboratory but is thought to be important in the gas phase synthesis of organic molecules in dense interstellar clouds. This reaction was studied theoretically by performing quantum chemical ab initio calculations on the potential surface. It is found that there is no activation barrier to the reaction and that it proceeds smoothly to the first excited electronic state of CH(+). The rate coefficient as a function of temperature can then be estimated using the proper long-range potentials. The rate coefficient at 10 K is calculated to be 2.9 x 10 to the -9th cu cm/sec.
Following a suggestion of Blake et al. (1987), an attempt was made to account for the unusually large abundances of selected oxygen-containing organic molecules in the so-called 'compact ridge' source directed toward Orion KL by a gas-phase chemical model in which large amounts of water are injected into the source from the IRc2 outflow. Although quantitative model results show that the calculated abundances of methanol, methyl formate, and dimethyl ether can be enhanced relative to their values in the absence of water injection, the enhancements fall far short of explaining the very large observed abundances of these species. Models in which methanol is injected rather than water are more successful, although the source of the methanol is unclear.
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.
A total of 414 previously unobserved millimeter- and submillimeter-wave transitions of (C-12)H3OH through J = 10 and v(t) = 2 are assigned. These data and previous measured spectral transitions are combined and fitted by a modified internal axis method (IAM) treatment in which the A and E substates are treated separately and a wide variety of new rotational-torsional interaction terms are employed. The modified IAM treatment reduces the overall rms deviation of the fits to the level of experimental accuracy. The resultant spectroscopic constants allow for the accurate prediction of 569 additional transitions through J = 12 or less.
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.
A mechanism for the enhanced splitting detected in the millimeter-wave rotational spectra of the first excited S-S stretching state of HSSH (disulfane) has been studied. The mechanism, which involves a potential coupling between the first excited S-S stretching state and excited torsional states, has been investigated in part by the use of ab initio theory. Based on an ab initio potential surface, coupling matrix elements have been calculated, and the amount of splitting has then been estimated by second-order perturbation theory. The result, while not in quantitative agreement with the measured splitting, lends plausibility to the assumed mechanism.