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Register a new userA rotational and vibrational investigation of phenylpropiolonitrile (C$_6$H$_5$C$_3$N)
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Added by
Kin Long Kelvin Lee
Publication date
2021
fields
Physics
and research's language is
English
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The evidence for benzonitrile (C$_6$H$_5$CN}) in the starless cloud core TMC-1 makes high-resolution studies of other aromatic nitriles and their ring-chain derivatives especially timely. One such species is phenylpropiolonitrile (3-phenyl-2-propynenitrile, C$_6$H$_5$C$_3$N), whose spectroscopic characterization is reported here for the first time. The low resolution (0.5 cm$^{-1}$) vibrational spectrum of C$_6$H$_5$C$_3$N} has been recorded at far- and mid-infrared wavelengths (50 - 3500 cm$^{-1}$) using a Fourier Transform interferometer, allowing for the assignment of band centers of 14 fundamental vibrational bands. The pure rotational spectrum of the species has been investigated using a chirped-pulse Fourier transform microwave (FTMW) spectrometer (6 - 18 GHz), a cavity enhanced FTMW instrument (6 - 20 GHz), and a millimeter-wave one (75 - 100 GHz, 140 - 214 GHz). Through the assignment of more than 6200 lines, accurate ground state spectroscopic constants (rotational, centrifugal distortion up to octics, and nuclear quadrupole hyperfine constants) have been derived from our measurements, with a plausible prediction of the weaker bands through calculations. Interstellar searches for this highly polar species can now be undertaken with confidence since the astronomically most interesting radio lines have either been measured or can be calculated to very high accuracy below 300 GHz.
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Electronic spectra of C$_6$H are measured in the $18,950-21,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $ u_6$ mode associated with the C-C bond vibration and the $ u_4$ and $ u_3$ modes associated with C$equiv$C triple bonds. For the two lowest $ u_{11}$ and $ u_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $mu^2Sigma$($ u_{11}$) and both $mu^2Sigma$($ u_{10}$) and $kappa^2Sigma$($ u_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $mu^2Sigma$($ u_9$) and $mu^2Sigma$($ u_8$) levels. In the excitation region below the first non-degenerate vibration ($ u_6$), some $^2Pi-^{2}Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2Pi-^{2}Pi$ transition found above the $ u_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2Pi$ state of C$_6$H is derived and presented.
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.
The chemical pathways linking the small organic molecules commonly observed in molecular clouds to the large, complex, polycyclic species long-suspected to be carriers of the ubiquitous unidentified infrared emission bands remain unclear. To investigate whether the formation of mono- and poly-cyclic molecules observed in cold cores could form via the bottom-up reaction of ubiquitous carbon-chain species with, e.g. atomic hydrogen, a search is made for possible intermediates in data taken as part of the GOTHAM (GBT Observations of TMC-1 Hunting for Aromatic Molecules) project. Markov-Chain Monte Carlo (MCMC) Source Models were run to obtain column densities and excitation temperatures. Astrochemical models were run to examine possible formation routes, including a novel grain-surface pathway involving the hydrogenation of C$_6$N and HC$_6$N, as well as purely gas-phase reactions between C$_3$N and both propyne (CH$_3$CCH) and allene (CH$_2$CCH$_2$), as well as via the reaction CN + H$_2$CCCHCCH. We report the first detection of cyanoacetyleneallene (H$_2$CCCHC$_3$N) in space toward the TMC-1 cold cloud using the Robert C. Byrd 100 m Green Bank Telescope (GBT). Cyanoacetyleneallene may represent an intermediate between less-saturated carbon-chains, such as the cyanopolyynes, that are characteristic of cold cores and the more recently-discovered cyclic species like cyanocyclopentadiene. Results from our models show that the gas-phase allene-based formation route in particular produces abundances of H$_2$CCCHC$_3$N that match the column density of $2times10^{11}$ cm$^{-2}$ obtained from the MCMC Source Model, and that the grain-surface route yields large abundances on ices that could potentially be important as precursors for cyclic molecules.
After the previous discovery of MgC$_3$N and MgC$_4$H in IRC+10216, a deeper Q-band (31.0-50.3 GHz) integration on this source had revealed two additional series of harmonically related doublets that we assigned on the basis of quantum mechanical calculations to the larger radicals MgC$_5$N and MgC$_6$H. The results presented here extend and confirm previous results on magnesium-bearing molecules in IRC,+10216. We derived column densities of (4.7$pm$1.3)$times$10$^{12}$ for MgC$_5$N and (2.0$pm$0.9)$times$10$^{13}$ for MgC$_6$H, which imply that MgC$_5$N/MgC$_3$N=0.5 and MgC$_6$H/MgC$_4$H = 0.9. Therefore, MgC$_5$N and MgC$_6$H are present with column densities not so different from those of the immediately shorter analogs. The synthesis of these large magnesium cyanides and acetylides in IRC+10216 can be explained for their shorter counterparts by a two-step process initiated by the radiative association of Mg$^+$ with large cyanopolyynes and polyynes, which are still quite abundant in this source, followed by the dissociative recombination of the ionic complexes.
The electron paramagnetic resonance study for an organic superconductor $beta$-(BEDT-TTF)$_{4}$[(H$_3$O)Ga(C$_2$O$_4$)$_3$]$cdot$C$_6$H$_5$NO$_2$ reveals that superconductivity coexists uniformly with the charge ordered state in one material. In the charge ordered state, the interplane spin exchange is gapped, while the in-plane conductivity is not significantly modified. This anisotropic behavior is explained by the exotic charge ordered state, in which molecular-site selective carrier localization coexists with conducting carriers on other molecules. Relationship between superconductivity and this conductive charge ordered state is investigated.
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