1,721,019 research outputs found
Dipolar spin–spin coupling as an auxiliary tool for the structure determination of small isolated molecules
Full text linkThe ‘‘gold standard’’ for obtaining accurate equilibrium structures is the so-called semi-experimental (SE) approach, which exploits the structural information contained in rotational constants. Within the SE approach, ground-state rotational constants—accurately obtained from high-resolution spectroscopic
studies—are computationally corrected in order to remove vibrational effects. The resulting SE equilibrium rotational constants for a significant set of isotopic species allow for retrieving a unique set of equilibrium bond lengths and angles for the molecule under consideration. However, in some cases, the lack of isotopic substitution hampers or even prevents a rigorous and complete structure determination. In this perspective, we introduce the use of dipolar spin–spin coupling constants as an additional source of structural information in support of the standard SE approach. As a proof-of-concept, we tested this new strategy on some prototypical species, such as water, ammonia, phosphine, Received 7th March 2022, Accepted 16th May 2022and their fluorinated counterparts. Our results indicate that—even when the molecular structure can be obtained from a large set of isotopic rotational constants—the use of dipolar spin–spin coupling constants guarantees a better accuracy and reduces the correlations among the geometrical parameters. Moreover, we point out that our approach offers the possibility to fully derive the molecular structure of PF3, a species for which any isotopic substitution is not possible
Hyperfine resolved rate coefficients of HC17O+ with H2 (j = 0)
Full text linkThe formyl cation (HCO+) is one of the most abundant ions in molecular clouds and plays a major role in the interstellar chemistry. For this reason, accurate collisional rate coefficients for the rotational excitation of HCO+ and its isotopes due to the most abundant perturbing species in interstellar environments are crucial for non-local thermal equilibrium models and deserve special attention. In this work, we determined the first hyperfine resolved rate coefficients of HC17O+ in collision with H2 (j = 0). Indeed, despite no scattering calculations on its collisional parameters have been performed so far, the HC17O+ isotope assumes a prominent role for astrophysical modelling applications. Computations are based on a new four dimensional (4D) potential energy surface obtained at the CCSD(T)-F12a/aug-cc-pVQZ level of theory. A test on the corresponding cross-section values pointed out that, to a good approximation, the influence of the coupling between rotational levels of H2 can be ignored. For this reason, the H2 collider has been treated as a spherical body and an average of the potential based on five orientations of H2 has been employed for scattering calculations. State-to-state rate coefficients resolved for the HC17O+ hyperfine structure for temperature ranging from 5 to 100K have been computed using recoupling techniques. This study provides the first determination of HC17O+–H2 inelastic rate coefficients directly computed from full quantum close-coupling equations, thus supporting the reliability of future radiative transfer modellings of HC17O+ in interstellar environments
The Semiexperimental Approach at Work: Equilibrium Structure of Radical Species
No full textThe so-called semiexperimental (SE) approach is a powerful technique for obtaining highly accurate equilibrium structures for isolated systems. This Featured Article describes its extension to open-shell species, thus providing the first systematic investigation on radical equilibrium geometries to be used for benchmarking purposes. The small yet significant database obtained demonstrates that there is no reduction in accuracy when moving from closed-shell species to radicals. We also provide an extension of the applicability of the SE approach to medium-/large-sized radicals by exploiting the so-called “Lego-brick” approach, which is based on the assumption that a molecular system can be seen as formed by smaller fragments for which the SE equilibrium structure is available. In this Featured Article we show that this model can be successfully applied also to open-shell species
Extension of the Lego-brick approach to protonated molecules
No full textWe take the opportunity to extend the applicability of the Lego-brick approach (that is, templating molecular systems from small fragments), by applying it to characterize structural properties of protonated molecules. We additionally present a new variant for it (LETSGO): instead of employing semi-experimental equilibrium geometries of fragments in the templating procedure, experimentally available structures are used. By comparison with experiment (rotational constants), we evaluate the performance of Lego-brick and LETSGO models on a significant range of systems. Our results appear to be a promising extension to techniques for generating equilibrium structures of protonated molecules
Exploiting the "Lego brick" approach to predict accurate molecular structures of PAHs and PANHs
Full text linkPolycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) are important and ubiquitous species in space. However, their accurate structural and spectroscopic characterization is often missing. To fill this gap, we exploit the so-called "Lego brick" approach [Melli et al., J. Phys. Chem. A, 2021, 125, 9904] to evaluate accurate rotational constants of some astrochemically relevant PAHs and PANHs. This model is based on the assumption that a molecular system can be seen as formed by smaller fragments for which a very accurate equilibrium structure is available. Within this model, the "template molecule" (TM) approach is employed to account for the modifications occurring when going from the isolated fragment to the molecular system under investigation, with the "linear regression" model being exploited to correct the linkage between different fragments. In the present work, semi-experimental equilibrium structures are used within the TM model. The performance of the "Lego brick" approach has been first tested for a set of small PA(N)Hs for which experimental data are available, thus leading to the conclusion that it is able to provide rotational constants with a relative accuracy well within 0.1%. Subsequently, it has been extended to the accurate prediction of the rotational constants for systems lacking any spectroscopic characterization
Terahertz Spectroscopy and Global Analysis of the Rotational Spectrum of Doubly Deuterated Amidogen Radical ND2
No full textThe deuteration mechanism of molecules in the interstellar medium is still being debated. Observations of
deuterium-bearing species in several astronomical sources represent a powerful tool to improve our understanding of the interstellar chemistry. The doubly deuterated form of the astrophysically interesting amidogen radical could be a target of detection in space. In this work, the rotational spectrum of the ND
2 radical in its ground vibrational and electronic X2B1state has been investigated between 588 and 1131 GHz using a frequency modulation millimeter/submillimeter-wave spectrometer. The ND2 molecule has been produced in a free-space glass absorption cell by discharging a mixture of ND3 and Ar. Sixty-four new transition frequencies involving J values from 2 to 5 and Ka values from 0 to 4 have been measured. A global analysis including all the previous field-free pure rotational data has been performed, allowing for a more precise determination of a very large number of spectroscopic parameters. Accurate predictions of rotational transition frequencies of ND2 are now available from a few gigahertz up to several terahertz
Hunting for interstellar molecules: rotational spectra of reactive species
Full text linkInterstellar molecules are often highly reactive species, which are unstable under terrestrial conditions, such as radicals, ions and unsaturated carbon chains. Their detection in space is usually based on the astronomical observation of their rotational fingerprints. However, laboratory investigations have to face the issue of efficiently producing these molecules and preserving them during rotational spectroscopy measurements. A general approach for producing and investigating unstable/reactive species is presented by means of selected case-study molecules. The overall strategy starts from quantum-chemical calculations that aim at obtaining accurate predictions of the missing spectroscopic information required to guide spectral analysis and assignment. Rotational spectra of these species are then recorded by exploiting the approach mentioned above, and their subsequent analysis leads to accurate spectroscopic parameters. These are then used for setting up accurate line catalogs for astronomical searches
Protonation of apolar species: from Cl2H+ to (E)-NCCHCHCNH+ through computational investigations
Full text linkRadioastronomy is a powerful tool for the discovery of molecules in space but it requires molecular species to be polar. The observation of apolar species can be however enabled by protonation, which occurs from reaction with the abundant H3+
ion whenever the proton affinity of the species under consideration is greater than that of H2. This property can be easily investigated by computational chemistry and, in this work, it has been used to asses the potential protonation of simple homo diatomics, such as Cl2, P2, and Si2, as well as apolar species containing two equivalent CN moieties, such as diisocyanogen (CNNC) and (E)-1,2-dicyanoethene. Quantum chemistry has also been exploited to investigate the mechanisms of three protonation reactions of H3+
with Cl2, P2, and CNNC. To support laboratory measurements and astronomical observations of the resulting transient species, their rotational spectroscopic parameters were accurately computed together with fundamental vibrational frequencies. For this purpose, we have employed CCSD(T)-based computational methodologies, which provide equilibrium structures with errors smaller than 0.001 Å and 0.1° for bond distances and angles, respectively. Such an accuracy is expected to lead to rotational constants predicted, in relative terms, with uncertainties better than 0.2%. Instead, the expected accuracy on vibrational frequencies is ∼10 cm−1, thus being well suited to guide band assignments
Hyperfine-resolved spectra of HDS together with a global ro-vibrational analysis
Full text linkDespite their chemical simplicity, the spectroscopic investigation of light hydrides, such as hydrogen sulfide, is challenging due to strong hyperfine interactions and/or anomalous centrifugal-distortion effects. Several hydrides have already been detected in the interstellar medium, and the list includes H2S and some of its isotopologues. Astronomical observation of isotopic species and, in particular, those bearing deuterium is important to gain insights into the evolutionary stage of astronomical objects and to shed light on interstellar chemistry. These observations require a very accurate knowledge of the rotational spectrum, which is so far limited for mono-deuterated hydrogen sulfide, HDS. To fill this gap, high-level quantum-chemical calculations and sub-Doppler measurements have been combined for the investigation of the hyperfine structure of the rotational spectrum in the millimeter- and submillimeter-wave region. In addition to the determination of accurate hyperfine parameters, these new measurements together with the available literature data allowed us to extend the centrifugal analysis using a Watson-type Hamiltonian and a Hamiltonian-independent approach based on the Measured Active Ro-Vibrational Energy Levels (MARVEL) procedure. The present study thus permits to model the rotational spectrum of HDS from the microwave to far-infrared region with great accuracy, thereby accounting for the effect of the electric and magnetic interactions due to the deuterium and hydrogen nuclei
Computational Protocol for the Identification of Candidates for Radioastronomical Detection and Its Application to the C<sub>3</sub>H<sub>3</sub>NO Family of Isomers
Full text linkThe C3H3NO family of isomers is relevant in astrochemistry, even though its members are still elusive in the interstellar medium. To identify the best candidate for astronomical detection within this family, we developed a new computational protocol based on the minimum-energy principle. This approach aims to identify the most stable isomer of the family and consists of three steps. The first step is an extensive investigation that characterizes the vast number of compounds having the C3H3NO chemical formula, employing density functional theory for this purpose. The second step is an energy refinement, which is used to select isomers and relies on coupled cluster theory. The last step is a structural improvement with a final energy refinement that provides improved energies and a large set of accurate spectroscopic parameters for all isomers lying within 30 kJ mol−1 above the most stable one. According to this protocol, vinylisocyanate is the most stable isomer, followed by oxazole, which is about 5 kJ mol−1 higher in energy. The other stable species are pyruvonitrile, cyanoacetaldehyde, and cyanovinylalcohol. For all of these species, new computed rotational and vibrational spectroscopic data are reported, which complement those already available in the literature or fill current gaps
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