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.

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.

The detection E-cyanomethanimine (E-HNCHCN) towards Sagittarius B2(N) is made by comparing the publicly available Green Bank Telescope (GBT) PRIMOS survey spectra (Hollis et al.) to laboratory rotational spectra from a reaction product screening experiment. The experiment uses broadband molecular rotational spectroscopy to monitor the reaction products produced in an electric discharge source using a gas mixture of NH 3 and CH 3 CN. Several transition frequency coincidences between the reaction product screening spectra and previously unassigned interstellar rotational transitions in the PRIMOS survey have been assigned to E-cyanomethanimine. A total of 8 molecular rotational transitions of this molecule between 9 and 50 GHz are observed with the GBT. Ecyanomethanimine, often called the HCN dimer, is an important molecule in prebiotic chemistry because it is a chemical intermediate in proposed synthetic routes of adenine, one of the two purine nucleobases found in DNA and RNA. New analyses of the rotational spectra of both E-cyanomethanimine and Zcyanomethanimine that incorporate previous mm-wave measurements are also reported.

Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor OO distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three-body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical OO distances are in good agreement. The cooperativity effects revealed by the hydrogen bond OO distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules.

The rotational spectrum of the higher-energy trans conformational isomer of methyl formate has been assigned for the first time using several pulsed-jet Fourier transform microwave spectrometers in the 6-60 GHz frequency range. This species has also been sought toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. We detect seven absorption features in the survey that coincide with laboratory transitions of trans-methyl formate, from which we derive a column density of 3.1 (+2.6, -1.2) × 10 13 cm -2 and a rotational temperature of 7.6 ± 1.5 K. This excitation temperature is significantly lower than that of the more stable cis conformer in the same source but is consistent with that of other complex molecular species recently detected in Sgr B2(N). The difference in the rotational temperatures of the two conformers suggests that they have different spatial distributions in this source. As the abundance of trans-methyl formate is far higher than would be expected if the cis and trans conformers are in thermodynamic equilibrium, processes that could preferentially form trans-methyl formate in this region are discussed. We also discuss measurements that could be performed to make this detection more certain. This manuscript demonstrates how publicly available broadband radio astronomical surveys of chemically rich molecular clouds can be used in conjunction with laboratory rotational spectroscopy to search for new molecules in the interstellar medium.

We have performed reaction product screening measurements using broadband rotational spectroscopy to identify rotational transition matches between laboratory spectra and the Green Bank Telescope PRIMOS radio astronomy survey spectra in Sagittarius B2 North (Sgr B2(N)).The broadband rotational spectrum of molecules created in an electrical discharge of CH 3 CN and H 2 S contained several frequency matches to unidentified features in the PRIMOS survey that did not have molecular assignments based on standard radio astronomy spectral catalogs. Several of these transitions are assigned to the E-and Z-isomers of ethanimine. Global fits of the rotational spectra of these isomers in the range of 8 to 130 GHz have been performed for both isomers using previously published mm-wave spectroscopy measurements and the microwave measurements of the current study. Possible interstellar chemistry formation routes for E-ethanimine and Z-ethanimine are discussed. The detection of ethanimine is significant because of its possible role in the formation of alanineone of the twenty amino acids in the genetic code.

The structures of the phenol dimer and phenol trimer complexes in the gas phase have been determined using chirped-pulse Fourier transform microwave spectroscopy in the 2-8 GHz band. All fourteen (13)C and (18)O phenol dimer isotopologues were assigned in natural abundance. A full heavy atom experimental substitution structure was determined, and a least-squares fit ground state r0 structure was determined by proper constraint of the M06-2X/6-311++g(d,p) ab initio structure. The structure of phenol dimer features a water dimer-like hydrogen bond, as well as a cooperative contribution from inter-ring dispersion. Comparisons between the experimental structure and previously determined experimental structures, as well as ab initio structures from various levels of theory, are discussed. For phenol trimer, a C3 symmetric barrel-like structure is found, and an experimental substitution structure was determined via measurement of the six unique (13)C isotopologues. The least-squares fit rm((1)) structure reveals a similar interplay between hydrogen bonding and dispersion in the trimer, with water trimer-like hydrogen bonding and C-H···π interactions.

No abstract