A new instrumentation for simultaneous terahertz and mid-infrared spectroscopy in corrosive gaseous mixtures.

The correct interpretation of infrared (IR) observations of planetary atmospheres requires an accurate knowledge of temperature and partial and global pressures. Precise laboratory measurements of absorption intensities and line profiles, in the 200-350 K temperature range, are, therefore, critical. However, for gases only existing in complex chemical equilibria, such as nitrous or hypobromous acids, it is not possible to rely on absolute pressure measurements to measure absolute integrated optical absorption cross sections or IR line intensities. To overcome this difficulty, a novel dual-beam terahertz (THz)/mid-IR experimental setup has been developed, relying on the simultaneous use of two instruments. The setup involves a newly constructed temperature-controlled (200-350 K) cross-shaped absorption cell made of inert materials. The cell is traversed by the mid-IR beam from a high-resolution Fourier transform spectrometer using along a White-cell optical configuration providing absorption path lengths from 2.8 to 42 m and by a THz radiation beam (82.5 GHz to 1.1 THz), probing simultaneously the same gaseous sample. The THz channel records pure rotational lines of molecules for which the dipole moment was previously measured with high precision using Stark spectroscopy. This allows for a determination of the partial pressure in the gaseous mixture and enables absolute line intensities to be retrieved for the mid-IR range. This new instrument opens a new possibility for the retrieval of spectroscopic parameters for unstable molecules of atmospheric interest. The design and performance of the equipment are presented and illustrated by an example of simultaneous THz and mid-IR measurement on nitrous acid (HONO) equilibrium.

High-Resolution Infrared Synchrotron Investigation of (HCN)2 and a Semi-Experimental Determination of the Dissociation Energy D0.

The high-resolution infrared absorption spectrum of the donor bending fundamental band ν 61 of the homodimer (HCN)2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν 61 transition has the typical appearance of a perpendicular type band associated with a Σ-Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν0 of 779.05182(50) cm-1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm-1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol-1 . The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19, 3257-3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol-1 for the dissociation energy D0 of this prototypical homodimer.

High-resolution synchrotron terahertz investigation of the large-amplitude hydrogen bond librational band of (HCN)2.

The high-resolution terahertz absorption spectrum of the large-amplitude intermolecular donor librational band ν of the homodimer (HCN)2 has been recorded by means of long-path static gas-phase Fourier transform spectroscopy at 207 K employing a highly brilliant electron storage ring source. The rovibrational structure of the ν band has the typical appearance of a perpendicular type band of a Σ-Π transition for a linear polyatomic molecule. The generated terahertz spectrum is analyzed employing a standard semi-rigid linear molecule Hamiltonian, yielding a band origin ν0 of 119.11526(60) cm-1 together with values for the excited state rotational constant B', the excited state quartic centrifugal distortion constant DJ' and the l-type doubling constant q for the degenerate state associated with the ν mode. The until now missing donor librational band origin enables the determination of an accurate experimental value for the vibrational zero-point energy of 2.50 ± 0.05 kJ mol-1 arising from the entire class of large-amplitude intermolecular modes. The spectroscopic findings are complemented by CCSD(T)-F12b/aug-cc-pV5Z (electronic energies) and CCSD(T)-F12b/aug-cc-pVQZ (force fields) electronic structure calculations, providing a (semi)-experimental value of 17.20 ± 0.20 kJ mol-1 for the dissociation energy D0 of this strictly linear weak intermolecular CHN hydrogen bond.

Direct Observation of Spatiotemporal Dynamics of Short Electron Bunches in Storage Rings.

In recent synchrotron radiation facilities, the use of short (picosecond) electron bunches is a powerful method for producing giant pulses of terahertz coherent synchrotron radiation. Here we report on the first direct observation of these pulse shapes with a few picoseconds resolution, and of their dynamics over a long time. We thus confirm in a very direct way the theories predicting an interplay between two physical processes. Below a critical bunch charge, we observe a train of identical THz pulses (a broadband Terahertz comb) stemming from the shortness of the electron bunches. Above this threshold, a large part of the emission is dominated by drifting structures, which appear through spontaneous self-organization. These challenging single-shot THz recordings are made possible by using a recently developed photonic time stretch detector with a high sensitivity. The experiment has been realized at the SOLEIL storage ring.

High sensitivity photonic time-stretch electro-optic sampling of terahertz pulses.

Single-shot recording of terahertz electric signals has recently become possible at high repetition rates, by using the photonic time-stretch electro-optic sampling (EOS) technique. However the moderate sensitivity of time-stretch EOS is still a strong limit for a range of applications. Here we present a variant enabling to increase the sensitivity of photonic time-stretch for free-propagating THz signals. The ellipticity of the laser probe is enhanced by adding a set of Brewster plates, as proposed by Ahmed et al. [Rev. Sci. Instrum. 85, 013114 (2014)] in a different context. The method is tested using the high repetition rate terahertz coherent synchrotron radiation source of the SOLEIL synchrotron radiation facility. The signal-to-noise ratio of our terahertz digitizer could thus be straightforwardly improved by a factor ≈6.5, leading to a noise-equivalent input electric field below 1.25 V/cm inside the electro-optic crystal, over the 0-300 GHz band (i.e., 2.3 µV/cm/Hz). The sensitivity is scalable with respect to the available laser power, potentially enabling further sensitivity improvements when needed.

Observing microscopic structures of a relativistic object using a time-stretch strategy.

Emission of light by a single electron moving on a curved trajectory (synchrotron radiation) is one of the most well-known fundamental radiation phenomena. However experimental situations are more complex as they involve many electrons, each being exposed to the radiation of its neighbors. This interaction has dramatic consequences, one of the most spectacular being the spontaneous formation of spatial structures inside electrons bunches. This fundamental effect is actively studied as it represents one of the most fundamental limitations in electron accelerators, and at the same time a source of intense terahertz radiation (Coherent Synchrotron Radiation, or CSR). Here we demonstrate the possibility to directly observe the electron bunch microstructures with subpicosecond resolution, in a storage ring accelerator. The principle is to monitor the terahertz pulses emitted by the structures, using a strategy from photonics, time-stretch, consisting in slowing-down the phenomena before recording. This opens the way to unpreceeded possibilities for analyzing and mastering new generation high power coherent synchrotron sources.

A combined experimental and theoretical study of the Ti2 + N2O reaction.

The reactivity of diatomic titanium with nitrous oxide has been studied in solid neon. Two molecules with the same Ti2-N2O stoichiometry are identified from concentration, temperature, and irradiation effects. The more stable one is characterized by five fundamental vibrational transitions located below 1000 cm(-1), the high frequency one at 946 cm(-1) corresponding to a pure TiO stretching mode. Its structure, a rhombus OTiNTiN with the extra O atom fixed on one Ti, is confirmed by quantum chemical calculations, at the CCSD(T) level, which predict a Cs structure in the singlet state with a Ti-O bond length close to 1.66 Å, two nonequivalent Ti-N distances close to 1.94 and 1.75 Å, and a OTiTi angle of 119.2°. The second Ti2-N2O molecule, only observed after annealing, is easily converted into the first one upon irradiation above 12 000 cm(-1) and its kinetics of photoconversion allows vibrational transitions to be identified. The strongest one located at 2123.4 cm(-1) characterizes an N-N stretching mode. Corresponding ab initio calculations complete this picture with details on the electronic structure and allow us to identify a most adequate density functional to describe the spectroscopic properties of the studied species in a simpler broken-symmetry open-shell DFT context. The theoretical results predict the existence of a metastable product OTi2N2 and correctly account for the observed spectra of the various isotopic varieties.

Resolving the forbidden band of SF6.

Sulfur hexafluoride is an important molecule for modeling thermophysical and polarizability properties. It is also a potent greenhouse gas of anthropogenic origin, whose concentration in the atmosphere, although very low is increasing rapidly; its global warming power is mostly conferred by its strong infrared absorption in the ν3 S-F stretching region near 948 cm(-1). This heavy species, however, features many hot bands at room temperature (at which only 31% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v6 = 1 vibrational state. Unfortunately, the ν6 band itself (near 347 cm(-1)), in the first approximation, is both infrared- and Raman-inactive, and no reliable spectroscopic information could be obtained up to now and this has precluded a correct modeling of the hot bands. It has been suggested theoretically and experimentally that this band might be slightly activated through Coriolis interaction with infrared-active fundamentals and appears in high pressure measurements as a very faint, unresolved band. Using a new cryogenic multipass cell with 93 m optical path length and regulated at 163 ± 2 K temperature, coupled to synchrotron radiation and a high resolution interferometer, the spectrum of the ν6 far-infrared region has been recorded. Low temperature was used to avoid the presence of hot bands. We are thus able to confirm that the small feature in this region, previously viewed at low-resolution, is indeed ν6. The fully resolved spectrum has been analyzed, thanks to the XTDS software package. The band appears to be activated by faint Coriolis interactions with the strong ν3 and ν4 fundamental bands, resulting in the appearance of a small first-order dipole moment term, inducing unusual selection rules. The band center (ν6 = 347.736707(35) cm(-1)) and rovibrational parameters are now accurately determined for the v6 = 1 level. The ν6 perturbation-induced dipole moment is estimated to be 33 ± 3 µD and the ν6 integrated intensity to be 0.0035 km mol(-1).

Coherent synchrotron radiation for broadband terahertz spectroscopy.

We present the first high resolution (10(-3) cm(-1)) interferometric measurements in the 200-750 GHz range using coherent synchrotron radiation, achieved with a low momentum compaction factor. The effect of microbunching on spectra is shown, depending on the bunch current. A high signal-to-noise ratio is reached thanks to an artifact correction system based on a double detection scheme. Combined to the broad emitted spectral range and high flux (up to 10(5) times the incoherent radiation), this study demonstrates that coherent synchrotron radiation can now be used for stability-demanding applications, such as gas-phase studies of unstable molecules.

Neon-matrix spectroscopic and theoretical studies of the reactivity of titanium dimer with diatomic ligands: comparison of reactions with nitrogen and carbon monoxide.

The reactivity of diatomic titanium with molecular carbon monoxide has been investigated in solid neon at very low temperature. In contrast to the spontaneous reaction observed between Ti(2) and N(2), our results show that the formation of dititanium oxycarbide (OTi(2)C) from the condensation of effusive beams of Ti and CO in neon matrices involves several intermediate steps including one metastable intermediate. In the absence of electronic excitation, only formation of a Ti(2)(CO) complex occurs spontaneously during the reaction at 9 K of ground state Ti(2) and CO, as reported in solid argon by Xu, Jiang and Tsumori (Angew. Chem. Int. Ed., 2005, 44, 4338). However, during deposition or following electronic excitation, this species rearranges into a new species: the more stable, OTi(2)C oxycarbide form. Several low-lying excited states of OTi(2)C are also observed between 0.77 and 0.89 eV above the ground state, leading to a complex sequence of interacting vibronic transitions, merging into a broad continuum above 1 eV. Observations of Ti(2)(12)C(16)O, Ti(2)(13)C(16)O and Ti(2)(12)C(18)O and natural titanium isotopic data enable the identification of four fundamental vibrations in the ground electronic state and two others in the first two excited states. Quantum chemical calculations predict an open-shell (1)A(g) ground state with Ti-C and Ti-O distances close to 184 pm, and 91 degrees for the TiCTi and TiOTi bond angles, and give fundamental frequencies in good agreement with observation. The reaction paths of the Ti(2) + N(2) --> Ti(2)N(2) and Ti(2) + CO --> Ti(2)(CO) --> OTi(2)C have been investigated and a reaction scheme is proposed accounting for the similarities in nature and properties of the final products, as well as explaining the observation of a coordination complex with Ti(2) only in the case of the carbonyl ligand.

Low-lying electronic states of the Ti2 dimer: electronic absorption spectroscopy in rare gas matrices in concert with quantum chemical calculations.

Absorption spectra were measured for Ti2 in Ne and Ar matrices. The spectra give evidence for several electronic transitions in the region between 4000 and 10 000 cm(-1) and provide important information about some excited electronic states of Ti2 in proximity to the ground state. The vibrational fine structure measured for these transitions allowed to calculate the force constants and the anharmonicity of the potential energy curves of the excited states, and to estimate changes in the internuclear Ti-Ti distances relative to the electronic ground state. The quantum chemical studies confirm the previously suggested (3)Delta(g) state as the ground state of Ti2. The equilibrium bond distance is calculated to be 195.4 pm. The calculated harmonic frequency of 432 cm(-1) is in good agreement with the experimental value of 407.0 cm(-1). With the aid of the calculations it was possible to assign the experimentally observed transitions in the region between 4000 and 10 000 cm(-1) to the 1 (3)Pi(u)<--(3)Delta(g), 1 (3)Phi(u)<--(3)Delta(g), 2 (3)Pi(u)<--(3)Delta(g), 2 (3)Phi(u)<--(3)Delta(g), and (3)Delta(u)<--(3)Delta(g) excitations (in the order of increasing energy). The calculated relative energies and harmonic frequencies are in pleasing agreement with the experimentally obtained values, with deviations of less than 5% and 2%, respectively. The bond distances estimated on the basis of the experimental spectra tally satisfactorily with the predictions of our calculations.