A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-C<sub>6</sub>H<sub>4</sub>-CN): benchmarking experiments and calculations using the “Lego brick” approach

Spaniol, Jean-Thibaut; Lee, Kelvin; Pirali, Olivier; Puzzarini, Cristina; Martin-Drumel, Marie-Aline

doi:10.1039/d2cp04825f

Cited by 6 publications

(8 citation statements)

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“…In line with Ye et al (2022), the computed B 0 values were found to deviate from experiment, on average, by 0.026%. The discrepancy increased to 2.5% for quartic centrifugal terms (Spaniol et al, 2023). The experimental spectroscopic data obtained by Spaniol et al (2023) will enable astronomical searches for these molecules.…”

Section: Figure 10mentioning

confidence: 96%

“…The discrepancy increased to 2.5% for quartic centrifugal terms (Spaniol et al, 2023). The experimental spectroscopic data obtained by Spaniol et al (2023) will enable astronomical searches for these molecules.…”

Section: Figure 10mentioning

confidence: 96%

“…A first application of the TM+LR model to systems of astrophysical interest in order to support their experimental characterization has been reported in Spaniol et al (2023), where the isomers of cyanoethynylbenzene (ortho−, meta− and para − HCC-C 6 H 4 -CN) have been considered. All of them are strong candidates for interstellar identification in view of the fact that benzonitrile (McGuire et al, 2018) and phenylacetylene (tentative; Cernicharo et al, 2021b) have already been detected, and both -CN and -CCH are polar and common functional groups.…”

Section: Toward Pahs and N-bearing Derivativesmentioning

confidence: 99%

“…For a stable and abundant molecule such as ammonia, the mono-deturated isotopologue (NH 2 D) has been considered (Melosso et al, 2020b;Melosso et al, 2021), which had to be prepared ad hoc inside the cell and allows for pointing out the importance of accounting for hyperfine effects in the rotational spectrum for the correct interpretation of astronomical spectra. Finally, a long carbon chain (DC 7 N; and isomers of cyanoethynylbenzene (Spaniol et al, 2023) have been taken as examples of larger systems.…”

Section: Introductionmentioning

confidence: 99%

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From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

Puzzarini,

Alessandrini,

Bizzocchi

et al. 2023

Front. Astron. Space Sci.

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The chemistry of the interstellar medium occurs under extreme conditions and can lead to the formation of exotic molecules. These are species that on Earth are unstable and/or highly reactive. Their discovery in space is usually based on the astronomical observation of their rotational fingerprints, which requires an accurate laboratory investigation. This is based on a strategy that starts from the interplay of experiment and theory. State-of-the-art quantum-chemical calculations are used to predict the relevant spectroscopic information required to guide the spectral recording, analysis and assignment. Rotational spectra measurements are then performed in the centimeter-/millimeter-/submillimeter-wave region, thereby exploiting efficient on-the-fly production protocols for exotic molecules. Subsequently, the spectral analysis leads to accurate spectroscopic parameters, which are then used for setting up accurate line catalogs for astronomical searches and detections. This review is based on the strategy developed and the results obtained at the ROT&Comp Lab of the University of Bologna.

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Section: Figure 10mentioning

confidence: 96%

Section: Figure 10mentioning

confidence: 96%

Section: Toward Pahs and N-bearing Derivativesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

Puzzarini,

Alessandrini,

Bizzocchi

et al. 2023

Front. Astron. Space Sci.

Self Cite

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“…In the previous decades, not only more computational resources have become available during the information revolution, but also the accuracy of quantum chemical calculations has been significantly increased, and is still improving continuously with newer and more elaborate theoretical conceptualizations. Several benchmarking studies involving tight collaborations between microwave spectroscopic and theoretical groups have been successfully established, aiming to predict the experimental rotational constants with even higher accuracy [12][13][14][15][16][17]. On the one hand, this joint-venture allows experimentalists to efficiently assign the microwave spectra and to access detailed molecular geometries in the cases when minor isotopologue spectra are lacking.…”

Section: Introductionmentioning

confidence: 99%

The Microwave Rotational Electric Resonance (RER) Spectrum of Benzothiazole

et al. 2023

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The microwave spectra of benzothiazole were measured in the frequency range 2–26.5 GHz using a pulsed molecular jet Fourier transform microwave spectrometer. Hyperfine splittings arising from the quadrupole coupling of the 14N nucleus were fully resolved and analyzed simultaneously with the rotational frequencies. In total, 194 and 92 hyperfine components of the main species and the 34S isotopologue, respectively, were measured and fitted to measurement accuracy using a semi-rigid rotor model supplemented by a Hamiltonian accounting for the 14N nuclear quadrupole coupling effect. Highly accurate rotational constants, centrifugal distortion constants, and 14N nuclear quadrupole coupling constants were deduced. A large number of method and basis set combinations were used to optimize the molecular geometry of benzothiazole, and the calculated rotational constants were compared with the experimentally determined constants in the course of a benchmarking effort. The similar value of the χcc quadrupole coupling constant when compared to other thiazole derivatives indicates only very small changes of the electronic environment at the nitrogen nucleus in these compounds. The small negative inertial defect of −0.056 uÅ2 hints that low-frequency out-of-plane vibrations are present in benzothiazole, similar to the observation for some other planar aromatic molecules.

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Accurate Geometries of Large Molecules at DFT Cost by Semiexperimental and Coupled Cluster Templating Fragments

Di Grande,

Lazzari,

Barone

2024

J. Chem. Theory Comput.

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Accurate geometries of small semirigid molecules in the gas phase are available thanks to high-resolution spectroscopy and accurate quantum chemical approaches. These results can be employed for validating cheaper lowlevel quantum chemical models or correcting the corresponding structures of large molecules. On these grounds, in this work, a large panel of semiexperimental equilibrium structures already available in the literature is used to confirm the average error (1 mÅ for bond lengths and 2 mrad for valence angles) of a version of the Pisa composite schemes (PCS2), which is applicable to molecules containing up to about 20 atoms. Then, the geometries of 30 additional mediumsized systems were optimized at the PCS2 level to cover a more balanced chemical space containing moieties poorly represented in SE compilations. The final database is available on a public domain Web site (https://www.skies-village.it/databases/) and can be employed for correcting structures of larger molecules obtained by hybrid or double-hybrid density functionals in the framework of the templating molecule approach. Several examples show that corrections based on the structures of building blocks taken from this database reduce the error of the B3LYP geometrical parameters of large molecules by nearly an order of magnitude without increasing the computational cost. Furthermore, the results of different density functional theory (DFT) or wave function (e.g., MP2) models can be improved in the same way by simply computing both the whole molecule and suitable building blocks at the chosen level. Then, whenever reference structures of some building blocks containing up to about 20 atoms are not available, they can be purposely optimized at the PCS2 level by employing reasonable computer resources. Therefore, a new DFT-cost tool is now available for the accurate characterization of large molecules by experiment-oriented scientists.

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A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-C₆H₄-CN): benchmarking experiments and calculations using the “Lego brick” approach

Abstract: The recent detection of several aromatic nitriles in the interstellar medium brings new interest into the laboratory spectroscopy of this family of molecules. Here, we report the study of three...

Cited by 6 publications

References 48 publications

From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

The Microwave Rotational Electric Resonance (RER) Spectrum of Benzothiazole

Accurate Geometries of Large Molecules at DFT Cost by Semiexperimental and Coupled Cluster Templating Fragments

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A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-C6H4-CN): benchmarking experiments and calculations using the “Lego brick” approach

Abstract: The recent detection of several aromatic nitriles in the interstellar medium brings new interest into the laboratory spectroscopy of this family of molecules. Here, we report the study of three...

Cited by 6 publications

References 48 publications

From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

From the laboratory to the interstellar medium: a strategy to search for exotic molecules in space

The Microwave Rotational Electric Resonance (RER) Spectrum of Benzothiazole

Accurate Geometries of Large Molecules at DFT Cost by Semiexperimental and Coupled Cluster Templating Fragments

Contact Info

Product

Resources

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A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-C₆H₄-CN): benchmarking experiments and calculations using the “Lego brick” approach