Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18-substituted water (H(2)(18)O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

We have searched for interstellar conformer I glycine (NH 2 CH 2 COOH), the simplest amino acid, in the hot molecular cores Sgr B2(N-LMH), Orion KL, and W51 e1/e2. An improved search strategy for intrinsically weak molecular lines, involving multisource observations, has been developed and implemented. In total, 82 spectral frequency bands, in the millimeter-wave region, were observed over a 4 yr period; 27 glycine lines were detected in 19 different spectral bands in one or more sources. The rotational temperatures derived from '' rotation diagrams '' are 75 þ29

Citation for published item:ihrdsonD teremy yF nd ¡ erezD grist¡ ol nd vosigerD imon nd eidD edm eF nd emelsoD ferhne nd hieldsD qeorge gF nd uisielD igniew nd lesD hvid tF nd teD frooks rF nd elthorpeD turt gF @PHITA 9gonerted hydrogenEond reking y quntum tunneling in the wter hexmer prismF9D ieneFD QSI @TPUWAF ppF IQIHEIQIQF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have changed the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13 C, 15 N, 18 O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2-8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H 2 O) 7 , in both 2-8 GHz and 6-18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to provide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H 2 18 O and HDO), and a least-squares r m (1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O-O equilibrium distances at the 0.01 Å level.

Context. Urea, NH 2 C(O)NH 2 , is a molecule of great importance in organic chemistry and biology. Two searches for urea in the interstellar medium have been reported in the past, but neither were conclusive. Aims. We want to take advantage of the increased sensitivity and angular resolution provided by the Atacama Large Millimeter/submillimeter Array (ALMA) to search for urea toward the hot molecular cores embedded in the high-mass-star-forming region Sgr B2(N). Methods. We used the new spectral line survey named ReMoCA (Re-exploring Molecular Complexity with ALMA) that was performed toward Sgr B2(N) with ALMA in its observing cycle 4 between 84 GHz and 114 GHz. The spectra were analyzed under the local thermodynamic equilibrium approximation. We constructed a full synthetic spectrum that includes all the molecules identified so far. We used new spectroscopic predictions for urea in its vibrational ground state and first vibrationally excited state to search for this complex organic molecule in the ReMoCA data set. We employed the gas-grain chemical kinetics model MAGICKAL to interpret the astronomical observations. Results. We report the secure detection of urea toward the hot core Sgr B2(N1) at a position called N1S slightly offset from the continuum peak, which avoids obscuration by the dust. The identification of urea relies on nine clearly detected transitions. We derive a column density of 2.7 × 10 16 cm −2 for urea, two orders of magnitude lower than the column density of formamide, and one order of magnitude below that of methyl isocyanate, acetamide, and N-methylformamide. The latter molecule is reliably identified toward N1S with 60 clearly detected lines, confirming an earlier claim of its tentative interstellar detection. We report the first interstellar detections of NH 2 CH 18 O and 15 NH 2 CHO. We also report the nondetection of urea toward the secondary hot core Sgr B2(N2) with an abundance relative to the other four species at least one order of magnitude lower than toward the main hot core. Our chemical model roughly reproduces the relative abundances of formamide, methyl isocyanate, acetamide, and N-methylformamide, but it overproduces urea by at least one order of magnitude. Conclusions. Urea is clearly detected in one of the hot cores. Comparing the full chemical composition of Sgr B2(N1S) and Sgr B2(N2) may help understand why urea is at least one order of magnitude less abundant in the latter source.

No abstract

No abstract

The recent analysis of the composition of the frozen surface of comet 67P/Churyumov-Gerasimenko has revealed a significant number of complex organic molecules. Methyl isocyanate (CH 3 NCO) is one of the more abundant species detected on the comet surface. In this work we report extensive characterization of its rotational spectrum resulting in a list of 1269 confidently assigned laboratory lines and its detection in space towards the Orion clouds where 399 lines of the molecule have been unambiguously identified. We find that the limited mm-wave laboratory data reported prior to our work require some revision. The abundance of CH 3 NCO in Orion is only a factor of ten below those of HNCO and CH 3 CN. Unlike the molecular abundances in the coma of comets, which correlate with those of warm molecular clouds, molecular abundances in the gas phase in Orion are only weakly correlated with those measured on the comet surface. We also compare our abundances with those derived recently for this molecule towards Sgr B2 (Halfen et al. 2015, ApJ, 812, L5). A more accurate abundance of CH 3 NCO is provided for this cloud based on our extensive laboratory work.