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Register a new userCumulene carbenes in TMC-1: Astronomical discovery of $l$-H$_2$C$_5$
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We report the first detection in space of the cumulene carbon chain $l$-H$_2$C$_5$. A total of eleven rotational transitions, with $J_{up}$ = 7-10 and $K_a$ = 0 and 1, were detected in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. We derive a column density of (1.8$pm$0.5)$times$10$^{10}$ cm$^{-2}$. In addition, we report observations of other cumulene carbenes detected previously in TMC-1, to compare their abundances with the newly detected cumulene carbene chain. We find that $l$-H$_2$C$_5$ is $sim$4.0 times less abundant than the larger cumulene carbene $l$-H$_2$C$_6$, while it is $sim$300 and $sim$500 times less abundant than the shorter chains $l$-H$_2$C$_3$ and $l$-H$_2$C$_4$. We discuss the most likely gas-phase chemical routes to these cumulenes in TMC-1 and stress that chemical kinetics studies able to distinguish between different isomers are needed to shed light on the chemistry of C$_n$H$_2$ isomers with $n$,$>$,3.
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The $1 ^3Sigma_u^- leftarrow X^3Sigma_g^-$ transition of linear HC$_5$H (A) has been observed in a neon matrix and gas phase. The assignment is based on mass-selective experiments, extrapolation of previous results of the longer HC$_{2n+1}$H homologues, and density functional and multi-state CASPT2 theoretical methods. Another band system starting at 303 nm in neon is assigned as the $1 ^1 A_1 leftarrow X ^1 A_1$ transition of the cumulene carbene pentatetraenylidene H$_2$C$_5$ (B).
Using radio observations with the Green Bank Telescope, evidence has now been found for a second five-membered ring in the dense cloud Taurus Molecular Cloud-1 (TMC-1). Based on additional observations of an ongoing, large-scale, high-sensitivity spectral line survey (GOTHAM) at centimeter wavelengths toward this source, we have used a combination of spectral stacking, Markov chain Monte Carlo (MCMC), and matched filtering techniques to detect 2-cyanocyclopentadiene, a low-lying isomer of 1-cyanocyclopentadiene, which was recently discovered there by the same methods. The new observational data also yields a considerably improved detection significance for the more stable isomer and evidence for several individual transitions between 23 - 32 GHz. Through our MCMC analysis, we derive total column densities of $8.3times10^{11}$ and $1.9times10^{11}$ cm$^{-2}$ for 1- and 2-cyanocyclopentadiene respectively, corresponding to a ratio of 4.4(6) favoring the former. The derived abundance ratios point towards a common formation pathway - most likely being cyanation of cyclopentadiene by analogy to benzonitrile.
We report the discovery of two unsaturated organic species, trans-(E)-cyanovinylacetylene and vinylcyanoacetylene, using the second data release of the GOTHAM deep survey towards TMC-1 with the 100 m Green Bank Telescope. For both detections, we performed velocity stacking and matched filter analyses using Markov chain Monte Carlo simulations, and for trans-(E)-cyanovinylacetylene, three rotational lines were observed at low signal-to-noise (${sim}$3$sigma$). From this analysis, we derive column densities of $2times10^{11}$ and $3times10^{11}$ cm$^{-2}$ for vinylcyanoacetylene and trans-(E)-cyanovinylacetylene, respectively, and an upper limit of $<2times10^{11}$ cm$^{-2}$ for trans-(Z)-cyanovinylacetylene. Comparisons with G3//B3LYP semi-empirical thermochemical calculations indicate abundances of the [H$_3$C$_5$N}] isomers are not consistent with their thermodynamic stability, and instead their abundances are mainly driven by dynamics. We provide discussion into how these species may be formed in TMC-1, with reference to related species like vinyl cyanide (CH$_2$=CHCN). As part of this discussion, we performed the same analysis for ethyl cyanide (CH$_3$CH$_2$CN), the hydrogenation product of CH$_2$=CHCN. This analysis provides evidence -- at 4.17$sigma$ significance -- an upper limit to the column density of $<4times10^{11}$ cm$^{-2}$; an order of magnitude lower than previous upper limits towards this source.
Polycyclic Aromatic Hydrocarbons (PAHs) have long been invoked in the study of interstellar and protostellar sources, but the unambiguous identification of any individual PAH has proven elusive until very recently. As a result, the formation mechanisms for this important class of molecules remain poorly constrained. Here we report the first interstellar detection of a pure hydrocarbon PAH, indene (C$_9$H$_8$), as part of the GBT Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) survey. This detection provides a new avenue for chemical inquiry, complementing the existing detections of CN-functionalized aromatic molecules. From fitting the GOTHAM observations, indene is found to be the most abundant organic ring detected in TMC-1 to date. And from astrochemical modeling with NAUTILUS, the observed abundance is greater than the models prediction by several orders of magnitude suggesting that current formation pathways in astrochemical models are incomplete. The detection of indene in relatively high abundance implies related species such as cyanoindene, cyclopentadiene, toluene, and styrene may be detectable in dark clouds.
We report structural and magnetic properties of the spin-$frac12$ quantum antiferromagnet Cu[C$_6$H$_2$(COO)$_4$][C$_2$H$_5$NH$_3$]$_2$ by means of single-crystal x-ray diffraction, magnetization, heat capacity, and electron spin resonance (ESR) measurements on polycrystalline samples, as well as band-structure calculations. The triclinic crystal structure of this compound features CuO$_4$ plaquette units connected into a two-dimensional framework through anions of the pyromellitic acid [C$_6$H$_2$(COO)$_4$]$^{4-}$. The ethylamine cations [C$_2$H$_5$NH$_3]^+$ are located between the layers and act as spacers. Magnetic susceptibility and heat capacity measurements establish a quasi-two-dimensional, weakly anisotropic and non-frustrated spin-$frac12$ square lattice with the ratio of the couplings $J_a/J_csimeq 0.7$ along the $a$ and $c$ directions, respectively. No clear signatures of the long-range magnetic order are seen in thermodynamic measurements down to 1.8,K. However, the gradual broadening of the ESR line suggests that magnetic ordering occurs at lower temperatures. Leading magnetic couplings are mediated by the organic anion of the pyromellitic acid and exhibit a non-trivial dependence on the Cu--Cu distance, with the stronger coupling between those Cu atoms that are further apart.
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