Christian P. Endres

Submillimeter-wave and far-infrared spectroscopy of high-J transitions of the ground and ν2=1 states of ammonia

Complete and reliable knowledge of the ammonia spectrum is needed to enable the analysis and interpretation of astrophysical and planetary observations. Ammonia has been observed in the interstellar medium up to J=18 and more highly excited transitions are expected to appear in hot exoplanets and brown dwarfs. As a result, there is considerable interest in observing and assigning the high J (rovibrational) spectrum. In this work, numerous spectroscopic techniques were employed to study its high J transitions in the ground and ν(2)=1 states. Measurements were carried out using a frequency multiplied submillimeter spectrometer at Jet Propulsion Laboratory (JPL), a tunable far-infrared spectrometer at University of Toyama, and a high-resolution Bruker IFS 125 Fourier transform spectrometer (FTS) at Synchrotron SOLEIL. Highly excited ammonia was created with a radiofrequency discharge and a dc discharge, which allowed assignments of transitions with J up to 35. One hundred and seventy seven ground state and ν(2)=1 inversion transitions were observed with microwave accuracy in the 0.3-4.7 THz region. Of these, 125 were observed for the first time, including 26 ΔK=3 transitions. Over 2000 far-infrared transitions were assigned to the ground state and ν(2)=1 inversion bands as well as the ν(2) fundamental band. Of these, 1912 were assigned using the FTS data for the first time, including 222 ΔK=3 transitions. The accuracy of these measurements has been estimated to be 0.0003-0.0006 cm(-1). A reduced root mean square error of 0.9 was obtained for a global fit of the ground and ν(2)=1 states, which includes the lines assigned in this work and all previously available microwave, terahertz, far-infrared, and mid-infrared data. The new measurements and predictions reported here will support the analyses of astronomical observations by high-resolution spectroscopy telescopes such as Herschel, SOFIA, and ALMA. The comprehensive experimental rovibrational energy levels reported here will permit further refinement of the potential energy surface to improve ammonia ab initio calculations and facilitate assignment of new high-resolution spectra of hot ammonia.

Application of superlattice multipliers for high-resolution terahertz spectroscopy

Frequency multipliers based on superlattice (SL) devices as nonlinear elements have been developed as radiation sources for a terahertz (THz) laboratory spectrometer. Input frequencies of 100 and 250 GHz from backward wave oscillators have been multiplied up to the 11th harmonic, producing usable frequencies up to 2.7 THz. Even at these high frequencies the output power is sufficient for laboratory spectroscopy. Comparisons to conventional high-resolution microwave spectroscopy methods reveal several superior features of this new device such as very high line frequency accuracies, broadband tunability, high output power levels at odd harmonics of the input frequency up to high orders, and a robust applicability.

Dimethyl ether: laboratory spectra up to 2.1 THz - Torsion-rotational spectra within the vibrational ground state

Dimethyl ether (CH3OCH3) is one of the largest organic molecules detected in the interstellar medium. As an asymmetric top molecule with two methyl groups which undergo large amplitude motions and a dipole moment of μ = 1.3 D, it conveys a dense spectrum throughout the terahertz region and contributes to the spectral line confusion in astronomical observations at these frequencies. In this paper, we present rotational spectra of dimethyl ether in its ground vibrational states, which have been measured in the laboratory and analyzed covering frequencies up to 2.1 THz. The analysis is based on an effective Hamiltonian for a symmetric two-top rotor and includes experimental data published so far. Frequency predictions are presented up to 2.5 THz for astronomical applications with accuracies better than 1 MHz.Dimethyl ether (CH3OCH3) is one of the largest organic molecules detected in the interstellar medium. As an asymmetric top molecule with two methyl groups which undergo large amplitude motions and a dipole moment of μ = 1.3 D, it conveys a dense spectrum throughout the terahertz region and contributes to the spectral line confusion in astronomical observations at these frequencies. In this paper, we present rotational spectra of dimethyl ether in its ground vibrational states, which have been measured in the laboratory and analyzed covering frequencies up to 2.1 THz. The analysis is based on an effective Hamiltonian for a symmetric two-top rotor and includes experimental data published so far. Frequency predictions are presented up to 2.5 THz for astronomical applications with accuracies better than 1 MHz.

High resolution rotational spectroscopy on D2O up to 2.7 THz in its ground and first excited vibrational bending states

We present highly accurate laboratory measurements on the pure rotational spectrum of doubly deuterated water, D2O, in selected frequency regions from 10 GHz up to 2.7 THz. Around 140 rotational transitions in both the vibrational ground and first excited bending states (upsilon2=0,1) were measured in total, involving energy levels with unexcelled high J and Ka rotational quantum numbers. The data give valuable information for the spectroscopic analysis of this molecule. In the case of the light and non-rigid water molecule, standard methods for its analysis are limited due to large centrifugal distortion interactions. Here, we present a global analysis of rotational and rovibrational data of the upsilon2=0 and 1 states of D2O by means of an Euler expansion of the Hamiltonian. In addition to the newly measured pure rotational transitions, around 4000 rotational and rovibrational lines have been included from previous work. It was possible to reproduce the extensive dataset to nearly its experimental uncertainty. The improved predictive capability of the model compared to previous work will be demonstrated.

High-resolution spectroscopy of C3 around 3 μm.

We report on the detection of the (10(0)1) ← (00(0)0) vibrational band of gas-phase C3 and the two of its mono (13)C substituted isotopologs in the infrared region around 3200 cm(-1). Additionally, the associated hot band (11(1)1) ← (01(1)0) has been assigned for the parent isotopolog. Spectra have been recorded using a supersonic jet spectrometer with a laser ablation source in combination with a continuous-wave optical parametric oscillator as radiation source. High-level quantum-chemical ab initio calculations have been performed and used to assist the assignment. A combined fit for the vibrational states of C3 found in this study has been done together with previously reported high-resolution data to increase the accuracy of the molecular parameters, especially for the ground state. The vibrational energies are 3260.126, 3205.593, and 3224.751 cm(-1) for the (10(0)1) state of C3, (12)C(13)C(12)C, and (13)C(12)C(12)C, respectively. The (11(1)1) state of C3 has been found to be at 3330.509 cm(-1).

High-Frequency Rotational Spectrum of Thioformaldehyde, H2CS, in the Ground Vibrational State

Pure rotational transitions have been measured for the normal isotopologue of thioformaldehyde, -->H212C32S , in the ground vibrational state in the 110-370 GHz, 570-670 GHz, and 850-930 GHz frequency ranges. A global data set has been constructed consisting of prior microwave and millimeter-wave transitions, the submillimeter-wave and terahertz (THz) transitions reported here, and far-infrared data and ground state combination differences. The 783 different transition frequencies in the data set were fit to Watsons S-reduced Hamiltonian with 20 parameters, resulting in a dimensionless weighted root-mean-square deviation of 0.78. New frequency predictions have been made for astronomical observations based on the molecular parameters obtained in the present study.

Dimethyl ether in its ground state, v = 0, and lowest two torsionally excited states, v11 = 1 and v15 = 1, in the high-mass star-forming region G327.3-0.6

Context. One of the big questions in astrochemistry is whether complex organic molecules are formed in the gas phase after evaporation of the icy mantles of interstellar dust grains or at intermediate temperatures within these icy mantles. Dimethyl ether (CH3OCH3) is one of these species that may form through either of these mechanisms, but it is yet unclear which is dominant. Aims. The goal of this paper is to determine the respective importance of solid state vs. gas phase reactions for the formation of dimethyl ether. This is done by a detailed analysis of the excitation properties of the ground state and the torsionally excited states, 311 = 1 and 315 = 1, toward the high-mass star-forming region G327.3-0.6. Methods. With the Atacama Pathfinder EXperiment 12 m submillimeter telescope, we performed a spectral line survey toward G327.3-0.6 around 1.3, 1.0, and 0.9 mm as well as at 0.43 and 0.37 mm. The observed CH3OCH3 spectrum is modeled assuming local thermal equilibrium. Results. CH3OCH3 has been detected in the ground state, 3 = 0, and in the torsionally excited states 311 = 1 and 315 = 1, for which lines have been detected here for the first time. The emission is modeled with an isothermal source structure as well as with a non-uniform spherical structure. In the isothermal case two components at 80 and 100 K are needed to reproduce the dimethyl ether emission, whereas an abundance jump at 85 K or a model with two abundance jumps at 70 and 100 K fit the emission equally well for the non-uniform source model. The emission from the torsionally excited states, 311 = 1 and 315 = 1, is very well fit by the same model as the ground state. Conclusions. For non-uniform source models one abundance jump for dimethyl ether is su cient to fit the emission, but two components are needed for the isothermal models. This suggests that dimethyl ether is present in an extended region of the envelope and traces a non-uniform density and temperature structure. Both types of models furthermore suggest that most dimethyl ether is present in gas that is warmer than 100 K, but a smaller fraction of 5%‐28% is present at temperatures between 70 and 100 K. The dimethyl ether present in this cooler gas is likely formed in the solid state, while gas phase formation probably is dominant above 100 K. Finally, the 311 = 1 and 315 = 1 torsionally excited states are easily excited under the density and temperature conditions in G327.3-0.6 and will thus very likely be detectable in other hot cores as well.

Laboratory rotational spectra of the dimethyl ether 13C-isotopologues up to 1.5 THz

Context. Dimethyl ether is found in high abundance in the interstellar medium. Owing to its strong and dense spectrum throughout the entire microwave and terahertz regime, it contributes to the spectral confusion in astronomical line surveys. The great sensitivity of new observatories like ALMA enhances the need for reliable spectroscopic data, especially for isotopic species of abundant molecules. In addition, the study of the interstellar C/C isotopic ratio can be used as a tracer of the formation process of a molecular species, and thus it gives insight into the chemical evolution of the observed region. Aims. The interpretation of astronomical observations depends on the knowledge of accurate rest frequencies and intensities. The objective of this work is to provide spectroscopic data for the two 13C-isotopologues of dimethyl ether in the vibrational ground state. Methods. High-resolution rotational-torsional spectra of CH3OCH3 and (CH3)2O have been measured in the laboratory covering frequencies up to 1.5 THz. The analysis is based on an effective rotational Hamiltonian for molecules with two large-amplitude motions. Results. Predictions of the complete ground state rotational spectrum of dimethyl ether-C1 and -C2 up to 2 THz are presented with accuracies better than 1 MHz. Based on the laboratory work, transitions of CH3OCH3 dimethyl ether have been detected for the first time in a large submillimeter line survey of the high-mass star forming region G327.3-0.6 performed with the APEX telescope.

The CDMS view on molecular data needs of Herschel, SOFIA, and ALMA

The catalog section of the Cologne Database for Molecular Spectroscopy, CDMS, contains mostly rotational transition frequencies, with auxiliary information, of molecules observable in space. The frequency lists are generated mostly from critically evaluated laboratory data employing established Hamiltonian models. The CDMS has been online publicly for more than 12 years, e.g., via the short-cut http://www.cdms.de. Initially constructed as ascii tables, its inclusion into a database environment within the Virtual Atomic and Molecular Data Centre (VAMDC, http://www.vamdc.eu) has begun in June 2008. A test version of the new CDMS is about to be released. The CDMS activities have been part of the extensive laboratory spectroscopic investigations in Cologne. Moreover, these activities have also benefit from collaborations with other laboratory spectroscopy groups as well as with astronomers. We will provide some basic information on the CDMS and its participation in the VAMDC project. In addition, some recent ...