No Arabic abstract
A better understanding of sulphur chemistry is needed to solve the interstellar sulphur depletion problem. A way to achieve this goal is to study new S-bearing molecules in the laboratory, obtaining accurate rest frequencies for an astronomical search. We focus on dithioformic acid, HCSSH, which is the sulphur analogue of formic acid. The aim of this study is to provide an accurate line list of the two HCSSH $trans$ and $cis$ isomers in their electronic ground state and a comprehensive centrifugal distortion analysis with an extension of measurements in the millimetre and submillimetre range. We studied the two isomers in the laboratory using an absorption spectrometer employing the frequency-modulation technique. The molecules were produced directly within a free-space cell by glow discharge of a gas mixture. We measured lines belonging to the electronic ground state up to 478 GHz, with a total number of 204 and 139 new rotational transitions, respectively, for $trans$ and $cis$ isomers. The final dataset also includes lines in the centimetre range available from literature. The extension of the measurements in the mm and submm range lead to an accurate set of rotational and centrifugal distortion parameters. This allows us to predict frequencies with estimated uncertainties as low as 5 kHz at 1 mm wavelength. Hence, the new dataset provided by this study can be used for astronomical search.
Observations of ammonia in interstellar environments have revealed high levels of deuteration, and all its D-containing variants, including ND$_3$, have been detected in cold prestellar cores and around young protostars. The observation of these deuterated isotopologues is very useful to elucidate the chemical and physical processes taking place during the very early stages of star formation, as the abundance of deuterated molecules is highly enhanced in dense and cold gas. Nitrogen hydride radicals are key species lying at the very beginning of the reaction pathway leading to the formation of NH$_3$ and organic molecules of pre-biotic interest, but relatively little information is known about their D-bearing isotopologues. To date, only ND has been detected in the interstellar gas. To aid the identification of further deuterated nitrogen radicals, we have thoroughly re-investigated the rotational spectrum of NHD employing two different instruments: a frequency-modulation submillimetre spectrometer operating in the THz region and a synchrotron-based Fourier Transform infrared spectrometer operating in the 50-240 cm$^{-1}$ wavelength range. NHD was produced in a plasma of NH$_3$ and D$_2$. A wide range of rotational energy levels has been probed thanks to the observation of high $N$ (up to 15) and high $K_a$ (up to 9) transitions. A global analysis including our new data and those already available in the literature has provided a comprehensive set of very accurate spectroscopic parameters. A highly reliable line catalogue has been generated to assist archival data searches and future astronomical observations of NHD at submillimetre and THz regimes.
As many organic molecules, formic acid (HCOOH) has two conformers (trans and cis). The energy barrier to internal conversion from trans to cis is much higher than the thermal energy available in molecular clouds. Thus, only the most stable conformer (trans) is expected to exist in detectable amounts. We report the first interstellar detection of cis-HCOOH. Its presence in ultraviolet (UV) irradiated gas exclusively (the Orion Bar photodissociation region), with a low trans-to-cis abundance ratio of 2.8+-1.0, supports a photoswitching mechanism: a given conformer absorbs a stellar photon that radiatively excites the molecule to electronic states above the interconversion barrier. Subsequent fluorescent decay leaves the molecule in a different conformer form. This mechanism, which we specifically study with ab initio quantum calculations, was not considered in Space before but likely induces structural changes of a variety of interstellar molecules submitted to UV radiation.
Very accurate transition frequencies of HC$_5$N were determined between 5.3 and 21.4 GHz with a Fourier transform microwave spectrometer. The molecules were generated by passing a mixture of HC$_3$N and C$_2$H$_2$ highly diluted in neon through a discharge valve followed by supersonic expansion into the Fabry-Perot cavity of the spectrometer. The accuracies of the data permitted us to improve the experimental $^{14}$N nuclear quadrupole coupling parameter considerably and the first experimental determination of the $^{14}$N nuclear spin-rotation parameter. The transition frequencies are also well suited to determine in astronomical observations the local speed of rest velocities in molecular clouds with high fidelity. The same setup was used to study HC$_7$N, albeit with modest improvement of the experimental $^{14}$N nuclear quadrupole coupling parameter. Quantum chemical calculations were carried out to determine $^{14}$N nuclear quadrupole and spin-rotation coupling parameters of HC$_5$N, HC$_7$N, and related molecules. These calculations included evaluation of vibrational and relativistic corrections to the non-relativistic equilibrium quadrupole coupling parameters; their considerations improved the agreement between calculated and experimental values substantially.
[Abridged] Investigations of neutron(n)-capture element nucleosynthesis and chemical evolution have largely been based on stellar spectroscopy. However, the recent detection of these elements in several planetary nebulae (PNe) indicates that nebular spectroscopy is a promising new tool for such studies. In PNe, n-capture element abundance determinations reveal details of s-process nucleosynthesis and convective mixing in evolved low-mass stars, as well as the chemical evolution of elements that cannot be detected in stellar spectra. Only one or two ions of a given trans-iron element can typically be detected in individual nebulae. Elemental abundance determinations thus require corrections for the abundances of unobserved ions. Such corrections rely on the availability of atomic data for processes that control the ionization equilibrium of nebulae. Until recently, these data were unknown for virtually all n-capture element ions. For the first five ions of Se, Kr, and Xe -- the three most widely detected n-capture elements in PNe -- we are calculating photoionization cross sections and radiative and dielectronic recombination rate coefficients using the multi-configuration Breit-Pauli atomic structure code AUTOSTRUCTURE. Charge transfer rate coefficients are being determined with a multichannel Landau-Zener code. To calibrate these calculations, we have measured absolute photoionization cross sections of Se and Xe ions at the Advanced Light Source synchrotron radiation facility. These atomic data can be incorporated into photoionization codes, which we will use to derive ionization corrections (hence abundances) for Se, Kr, and Xe in ionized nebulae. These results are critical for honing nebular spectroscopy into a more effective tool for investigating the production and chemical evolution of trans-iron elements in the Universe.
We numerically study the implementation of a NOT gate by laser pulses in a model molecular system presenting two electronic surfaces coupled by non adiabatic interactions. The two states of the bit are the fundamental states of the cis-trans isomers of the molecule. The gate is classical in the sense that it involves a one-qubit flip so that the encoding of the outputs is based on population analysis which does not take the phases into account. This gate can also be viewed as a double photo-switch process with the property that the same electric field controls the two isomerizations. As an example, we consider one-dimensional cuts in a model of the retinal in rhodopsin already proposed in the literature. The laser pulses are computed by the Multi Target Optimal Control Theory with chirped pulses as trial fields. Very high fidelities are obtained. We also examine the stability of the control when the system is coupled to a bath of oscillators modelled by an Ohmic spectral density. The bath correlation time scale being smaller than the pulse duration the dynamics is carried out in the Markovian approximation.