0000000000164103
AUTHOR
Gabriele Cazzoli
33S hyperfine interactions in H2S and SO2 and revision of the sulfur nuclear magnetic shielding scale
Using the Lamb-dip technique, the hyperfine structure in the rotational spectra of H2(33)S and (33)SO2 has been resolved and the corresponding parameters--that is, the sulfur quadrupole-coupling and spin-rotation tensors--were determined. The experimental parameters are in good agreement with results from high-level coupled-cluster calculations, provided that up to quadruple excitations are considered in the cluster operator, sufficiently large basis sets are used, and vibrational corrections are accounted for. The (33)S spin-rotation tensor for H2S has been used to establish a new sulfur nuclear magnetic shielding scale, combining the paramagnetic part of the shielding as obtained from the…
The hyperfine structure in the rotational spectrum of water: Lamb-dip technique and quantum-chemical calculations
Seven ortho rotational transitions have been recorded for the main isotopic species of water in the mil- limeter- and submillimeter-wave region using the Lamb-dip technique in order to resolve the hyperfine structure due to the hydrogens and to provide accurate hyperfine constants. The experimental determi- nation has been supplemented by high-level quantum-chemical calculations of the hyperfine parameters thereby focusing in particular on a systematic study of the basis-set convergence and on vibrational effects.
Rotational spectra of isotopic species of silyl fluoride. Part II: theoretical and empirical equilibrium structure
Abstract The equilibrium structure of silyl fluoride, SiH 3 F, has been reinvestigated using both theoretical and experimental data. With respect to the former, quantum-chemical calculations at the coupled-cluster level have been employed together with extrapolation to the basis set limit, consideration of higher excitations in the cluster operator, and inclusion of core correlation as well as relativistic corrections ( r (Si–F) = 1.5911 A, r (Si–H) = 1.4695 A, and ∠FSiH = 108.30°). A semi-experimental equilibrium structure has been determined based on the available rotational constants for the various isotopic species of silyl fluoride ( 28 SiH 3 F, 28 SiD 3 F, 29 SiH 3 F, 29 SiD 3 F, 30 S…
Microwave, High-Resolution Infrared, and Quantum Chemical Investigations of CHBrF2: Ground and v4 = 1 States
A combined microwave, infrared, and computational investigation of CHBrF(2) is reported. For the vibrational ground state, measurements in the millimeter- and sub-millimeter-wave regions for CH(79)BrF(2) and CH(81)BrF(2) provided rotational and centrifugal-distortion constants up to the sextic terms as well as the hyperfine parameters (quadrupole-coupling and spin-rotation interaction constants) of the bromine nucleus. The determination of the latter was made possible by recording of spectra at sub-Doppler resolution, achieved by means of the Lamb-dip technique, and supporting the spectra analysis by high-level quantum chemical calculations at the coupled-cluster level. In this context, the…
Hyperfine structure in the rotational spectra of trans-formic acid: Lamb-dip measurements and quantum-chemical calculations
Context. Formic acid, HCOOH, is the simplest organic acid and the first that has been identified in the interstellar medium. Its astrophysical relevance has motivated this spectroscopic study. Aims. The aim of this investigation is to provide very accurate rest frequencies for the trans isomer of HCOOH as well as to improve the spectroscopic and hyperfine parameters available in the literature for this molecule. Methods. The Lamb-dip technique has been exploited in order to record the rotational spectrum of trans-HCOOH at sub-Doppler resolution in the millimeter- and submillimeter-wave frequency ranges and, when possible, to resolve the hyperfine structure due to the hydrogen nuclei. THz me…
The rotational spectrum of 17O2 up to the THz region
Abstract The investigation of the pure rotational spectrum of the 17O2 isotopic species of molecular oxygen has been extended with respect to previous investigations to the submillimeter-wave region, from 230 GHz up to 1.06 THz. The resulting spectroscopic parameters, which have an accuracy comparable to that of the constants obtained from an updated isotopic invariant fit involving data for three electronic states and six isotopologues [Yu et al. High resolution spectral analysis of oxygen. IV. Energy levels, partition sums, bandconstants, RKR potentials, Franck–Condon factors involving the X 3 Σ g − , a 1 Δ g , and b 1 Σ g + states. J Chem Phys 2014;141:174302/1–12], permit the prediction…
Laboratory measurements and astronomical search for the HSO radical
[Context] Despite the fact that many sulfur-bearing molecules, ranging from simple diatomic species up to astronomical complex molecules, have been detected in the interstellar medium, the sulfur chemistry in space is largely unknown and a depletion in the abundance of S-containing species has been observed in the cold, dense interstellar medium. The chemical form of the missing sulfur has yet to be identified.
The hyperfine structure in the rotational spectra of bromofluoromethane: Lamb-dip technique and quantum-chemical calculations
International audience; The hyperfine structure in the rotational spectra of six isotopic species of bromofluoromethane, namely CH2{79}BrF, CH2{81}BrF, CDH{79}BrF, CDH{81}BrF, CD2{79}BrF, and CD2{81}BrF, has been investigated using the Lamb-dip technique in the submillimeter-wave frequency range. Measurements as well as assignment procedures have been supported by high-level quantum-chemical calculations of the hyperfine parameters at the coupled-cluster level. For all species, the accuracy of the determined rotational and centrifugal distortion constants as well as the bromine quadrupole-coupling constants have been improved with respect to available literature data, whereas the full bromi…
The hyperfine structure in the rotational spectra of D2(17)O and HD(17)O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen
Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing (17)O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimental…
The rotational spectrum of trans-DCOOD: Lamb-dip measurements, THz spectroscopy and quantum-chemical calculations
Abstract The rotational spectrum of the bi-deuterated isotopologue of trans-formic acid, trans-DCOOD, was recorded at sub-Doppler resolution in the millimeter- and sub-millimeter-wave region using the Lamb-dip technique. The hyperfine structure due to the deuterium nuclei could be resolved and accurate hyperfine constants were derived. The experimental determination of the deuterium quadrupole-coupling constants was supported by high-level quantum-chemical calculations at the coupled-cluster level using large atomic-orbital basis sets. The Lamb-dip measurements were also supplemented by THz Doppler-limited measurements in order to extend the predictive capability of the available spectrosco…
The rare isotopomers of HCN: HC15N and DC15N. Rotational spectrum and resolved nuclear hyperfine structures due to 15N and D.
In the present work the J + 1 ← J rotational transitions, with J = 0-7, of HC15N and the J + 1 ← J rotational transitions, with J = 0-7, 9, of DC15N have been investigated. The Lamb-dip technique has been employed in order to resolve the hyperfine structure due to deuterium and 15N. For HC15N, the hyperfine parameters have been determined for the first time. With respect to DC15N, only the spin rotation of 15N have been determined for the first time but a more reliable spin rotation of D has been obtained. The experimental evaluation of the hyperfine constants has been aided by highly accurate ab initio computations. Furthermore, the rotational transitions observed allowed us to provide the…
PRECISE LABORATORY MEASUREMENTS OF TRANS-DCOOH AND TRANS-HCOOD FOR ASTROPHYSICAL OBSERVATIONS
The rotational spectra of the mono-deuterated isotopologues of trans-formic acid, trans-DCOOH and trans-HCOOD, were investigated. In the millimeter- and submillimeter-wave frequency regions the Lamb-dip technique was exploited to obtain sub-Doppler resolution and to resolve the hyperfine structure due to the deuterium and hydrogen nuclei, thus enabling the accurate determination of the corresponding hyperfine constants. The experimental determination was supported by high-level quantum-chemical calculations at the coupled-cluster level of theory using large atomic-orbital basis sets. The Lamb-dip measurements were also supplemented by THz Doppler- limited measurements in order to extend the…
THE HYPERFINE STRUCTURE of the ROTATIONAL SPECTRUM of HDO and ITS EXTENSION to the THz REGION: ACCURATE REST FREQUENCIES and SPECTROSCOPIC PARAMETERS for ASTROPHYSICAL OBSERVATIONS
The rotational spectrum of the mono-deuterated isotopologue of water, HD16O, has been investigated in the millimeter- and submillimeter-wave frequency regions, up to 1.6 THz. The Lamb-dip technique has been exploited to obtain sub-Doppler resolution and to resolve the hyperfine (hf) structure due to the deuterium and hydrogen nuclei, thus enabling the accurate determination of the corresponding hf parameters. Their experimental determination has been supported by high-level quantum-chemical calculations. The Lamb-dip measurements have been supplemented by Doppler-limited measurements (weak high-J and high-frequency transitions) in order to extend the predictive capability of the available s…
Rotational spectra of CF+and13CF+: accurate rest frequencies and spectroscopic parameters
Context. The astrophysical relevance of the fluoromethylidynium ion and its importance for the interstellar chemistry of fluorine motivated the present laboratory spectroscopic investigation of both 12 CF + and the corresponding 13 C-containing isotopologue, 13 CF + . Aims. This investigation has been carried out to provide accurate rest frequencies for future (radioastronomical) observations, to improve the accuracy of the values for the spectroscopic parameters available in the literature for CF + , and to provide them for the first time for 13 CF + . Methods. Rotational spectra of CF + and 13 CF + were recorded in the millimeter- and submillimeter-wave frequency ranges. Their investigati…
Rotational spectra of isotopic species of silyl fluoride. Part I: Lamb-dip measurements and quantum-chemical calculations
The Lamb-dip technique has been employed for recording the rotational spectra of three isotopic species of silyl fluoride, namely (28)SiH3F, (29)SiH3F, and (30)SiH3F, in order to improve the knowledge of their spectro- scopic parameters as well as to try to resolve their hyperfine structure. High-level quantum-chemical computations using state-of-the-art coupled-cluster techniques together with core-polarized correla- tion-consistent basis sets have been employed to provide reliable reference values for the hyperfine parameters involved and have been used to guide the experimental investigation. Analysis of the exper- imental spectra allowed to improve the accuracy of the known spectroscopi…
Rare isotopic species of hydrogen sulfide: the rotational spectrum of H236S
The rotational spectrum of the 36 S-bearing isotopologue of hydrogen sulfide (H2S) has been investigated for the first time in the 167 GHz−1.6 THz frequency range, thus providing an accurate and reliable set of spectroscopic parameters. The experimental investigation was backed up by state-of-the-art quantum-chemical calculations, which also allowed us to demonstrate the incorrectness of the previously reported spectroscopic constants. The present results are of suitable accuracy to attempt the astrophysical detection of the isotopic species under consideration. Finally, reliable predictions for the spectroscopic constants of other rare isotopologues of H2S, namely the mono- and bi-deuterat…
Rotational spectrum of silyl chloride: hyperfine structure and equilibrium geometry
The Lamb-dip technique was employed to record the rotational spectra of two isotopic species of silyl chloride, namely (28)SiH3Cl and (29)SiH3Cl, in order to investigate their hyperfine structure. High-accuracy quantum-chemical computations were employed to predict the hyperfine parameters involved and to support the experimental investigation. Analysis of the experimental spectra led to an improvement in the accuracy of the known spectroscopic constants as well as allowed us to determine additional spectroscopic parameters for the first time. Furthermore, the equilibrium structure of silyl chloride was reinvestigated using both theoretical and experimental data. The best theoretical and se…
Zeeman effect in sulfur monoxide: A tool to probe magnetic fields in star forming regions
[Context] Magnetic fields play a fundamental role in star formation processes and the best method to evaluate their intensity is to measure the Zeeman effect of atomic and molecular lines. However, a direct measurement of the Zeeman spectral pattern from interstellar molecular species is challenging due to the high sensitivity and high spectral resolution required. So far, the Zeeman effect has been detected unambiguously in star forming regions for very few non-masing species, such as OH and CN.