0000000000008745
AUTHOR
Thomas F. Giesen
Mass-independent analysis of the stable isotopologues of gas-phase titanium monoxide – TiO
More than 130 pure rotational transitions of $^{46}$TiO, $^{47}$TiO, $^{48}$TiO, $^{49}$TiO, $^{50}$TiO, and $^{48}$Ti$^{18}$O are recorded using a high-resolution mm-wave supersonic jet spectrometer in combination with a laser ablation source. For the first time a mass-independent Dunham-like analysis is performed encompassing rare titanium monoxide isotopologues, and are compared to results from high-accuracy quantum-chemical calculations. The obtained parametrization reveals for titanium monoxide effects due to deviations from the Born-Oppenheimer approximation. Additionally, the dominant titanium properties enable an insight into the electronic structure of TiO by analyzing its hyperfin…
Gas-phase detection of HSOD and empirical equilibrium structure of oxadisulfane
We present the first gas phase spectra of singly deuterated oxadisulfane, HSOD, in its vibrational ground state. More than 100 transitions have been recorded with highest frequency accuracy using the Cologne Terahertz Spectrometer. The molecular parameters derived from a least squares fit analysis proof HSOD to be an almost accidental symmetric prolate top molecule with an asymmetry parameter kZK0.9985. Spectra of c-type and weaker b-type transitions have been recorded in the range from 716 to 772 GHz. The ratio of the dipole moments mc/mbZ2.4(3) has been derived from measured line intensities. The c-type transitions are split by the tunneling motion of a hindered internal rotation, whereas…
Gas-Phase Spectroscopic Detection and Structural Elucidation of Carbon-Rich Group 14 Binary Clusters: Linear GeC3Ge
Guided by high-level quantum-chemical calculations at the CCSD(T) level of theory, the first polyatomic germanium-carbon cluster, linear Ge2C3, has been observed at high spectral resolution in the gas phase through its remarkably complex fundamental antisymmetric C-C stretching mode ν3 located at 1932 cm(-1). The observation of a total of six isotopic species permits the derivation of a highly accurate value for the equilibrium Ge-C bond length. The present study suggests that many more Ge-C species might be detectable in the future using a combination of laser-ablation techniques for production and high-resolution infrared and/or microwave techniques for spectroscopic detection.
Opportunities for Fundamental Physics Research with Radioactive Molecules
Molecules containing short-lived, radioactive nuclei are uniquely positioned to enable a wide range of scientific discoveries in the areas of fundamental symmetries, astrophysics, nuclear structure, and chemistry. Recent advances in the ability to create, cool, and control complex molecules down to the quantum level, along with recent and upcoming advances in radioactive species production at several facilities around the world, create a compelling opportunity to coordinate and combine these efforts to bring precision measurement and control to molecules containing extreme nuclei. In this manuscript, we review the scientific case for studying radioactive molecules, discuss recent atomic, mo…
A mass-independent expanded Dunham analysis of aluminum monoxide and aluminum monosulfide
Abstract Pure rotational transitions of 27Al16O, 27Al18O, 27Al32S, and 27Al34S are recorded in the vibrational ground state and singly excited vibrational state using a mm-wavelength supersonic jet spectrometer in combination with a laser ablation source. In total 275 rotational transitions have been assigned. For the first time, mass-independent expanded Dunham analyses are performed using isotopologues of aluminum monoxide and aluminum monosulfide. The breakdown of the Born-Oppenheimer approximation is observed. Based on these mass-independent analyses, frequency positions of pure rotational transitions of the rare radioactive isotopologues 26AlO and 26AlS are predicted with uncertainties…
Infrared Spectroscopy of Disilicon-Carbide, Si2C: The ν3 Fundamental Band
The ν3 antisymmetric stretching mode of disilicon-carbide, Si2C, was studied using a narrow line width infrared quantum cascade laser spectrometer operating at 8.3 μm. The Si2C molecules were produ...
Rotational spectra and hyperfine structure of isotopic species of deuterated cyanoacetylene, DC3N
Abstract Cyanoacetylene enriched in deuterium was used to record pure rotational transitions of DC 3 N and its rare 13 C and 15 N isotopic species by employing Fourier transform microwave (FTMW) spectroscopy on a supersonic-jet expansion at centimeter wavelengths (8.2–25.4 GHz) and by using long-path absorption spectroscopy at millimeter and submillimeter wavelengths (82–900 GHz). In addition, submillimeter wave measurements (304–897 GHz) have been performed for DC 3 N in its v 7 = 1 lowest excited vibrational state. Hyperfine structure caused by the 14 N and D nuclei has been resolved in the FTMW spectra. Quantum-chemical calculations have been performed on the hyperfine structure paramete…
Spectroscopy of short-lived radioactive molecules
Molecular spectroscopy offers opportunities for the exploration of the fundamental laws of nature and the search for new particle physics beyond the standard model1–4. Radioactive molecules—in which one or more of the atoms possesses a radioactive nucleus—can contain heavy and deformed nuclei, offering high sensitivity for investigating parity- and time-reversal-violation effects5,6. Radium monofluoride, RaF, is of particular interest because it is predicted to have an electronic structure appropriate for laser cooling6, thus paving the way for its use in high-precision spectroscopic studies. Furthermore, the effects of symmetry-violating nuclear moments are strongly enhanced5,7–9 in molecu…
Isotope Shifts of Radium Monofluoride Molecules
Isotope shifts of $^{223-226,228}$Ra$^{19}$F were measured for different vibrational levels in the electronic transition $A^{2}{}{\Pi}_{1/2}\leftarrow X^{2}{}{\Sigma}^{+}$. The observed isotope shifts demonstrate the particularly high sensitivity of radium monofluoride to nuclear size effects, offering a stringent test of models describing the electronic density within the radium nucleus. Ab initio quantum chemical calculations are in excellent agreement with experimental observations. These results highlight some of the unique opportunities that short-lived molecules could offer in nuclear structure and in fundamental symmetry studies.
The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz
Abstract We present the first pure rotational spectra of the two most stable conformers of oxatrisulfane, trans- and cis-HSSOH, in their vibrational ground state. For both conformers a-, b-, and c-type transitions have been recorded in the range from 75 to 120 GHz using an all solid-state spectrometer. More than 200 lines have been assigned for each conformer, most of them belonging to the r Q 2 - and the r Q 3 -branch of the perpendicular spectra. The least-squares fit analysis using a semirigid rotor Hamiltonian in S-reduction yields precise values for the ground-state rotational constants A 0 = 21 145.93422 ( 66 ) , B 0 = 4479.92301 ( 21 ) , C 0 = 3828.34269 ( 21 ) for cis-HSSOH, and A 0…
Determination of accurate rest frequencies and hyperfine structure parameters of cyanobutadiyne, HC5N
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 molecula…