A rotational and vibrational investigation of phenylpropiolonitrile (C6H5C3N)

Buchanan, Zachary; Lee, Kelvin; Chitarra, Olivia; McCarthy, Michael; Pirali, Olivier; Martin‐Drumel, Marie‐Aline

doi:10.1016/j.jms.2021.111425

Cited by 13 publications

(22 citation statements)

References 34 publications

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“…During the preparation of this manuscript, we became aware of the spectroscopic characterization of 3-phenyl-2-propynenitrile (PPN). 75 Since—as noted above—the TM-SE approach works extremely well for rather rigid molecules, we decided to apply it to the structural determination of PPN and its isomers, thus providing an example of extension of the TM-SE approach to a larger system. For PPN, the resulting structure is shown in Figure 5 , with the corresponding rotational constants being collected in Table 3 .…”

Section: Resultsmentioning

confidence: 99%

“… a The relative differences with respect to SE( B e SE ) are reported in parentheses. b Ground-state rotational constants from ref ( 75 ) corrected for vibrational corrections at the B3 level. …”

Section: Resultsmentioning

confidence: 99%

“… b Ground-state rotational constants from ref ( 75 ) corrected for vibrational corrections at the B3 level. …”

Section: Resultsmentioning

confidence: 99%

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Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

et al. 2021

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The accurate determination of equilibrium structures for isolated molecules plays a central role in the evaluation and interpretation of stereoelectronic, thermodynamic, and spectroscopic properties. For small semi-rigid systems, state-of-the-art quantum-chemical computations can rival the most sophisticated experimental results. For larger molecules, cheaper yet accurate approaches need to be defined. The double-hybrid rev-DSD-PBEP86 functional already delivers remarkable results that can be further improved by means of a “Lego brick” model. This is based on the idea that a molecular system can be seen as formed by different fragments (the “Lego bricks”), whose accurate semi-experimental (SE) equilibrium geometries are available. The template molecule (TM) approach can be used to account for the modifications occurring when going from the isolated fragment to the molecular system under investigation, with the linear regression (LR) model employed to correct the linkage between the different fragments. The resulting TM-SE_LR approach has been tested with respect to available SE equilibrium structures and rotational constants. Indeed, the latter parameters straightforwardly depend on the equilibrium geometry of the system under consideration. The main outcome of our study is the reliability, robustness, and accuracy of this novel approach. The molecular systems considered for benchmarking the TM-SE_LR scheme are those formally issued from addition/elimination reactions of nucleophilic unsaturated radicals (e.g., CN, C2H, and phenyl) to alkenes, imines, and aldehydes, whose rotational spectra have been investigated, but accurate structural determinations are not yet available.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

et al. 2021

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“…While taking interstellar detection into the consideration, the hyperfine resolved structure might play a significant role for the considered PANH species as the splitting in the cm-wave region is found to be similar with the linewidths measured for a typical cold, dark molecular clouds-e.g., TMC-1 (Buchanan et al 2021). Therefore, the 14 N quadrupole hyperfine resolved structures are also given for the strongest transitions of the considered N-and CN-PAH molecules at 5, 10 and 100 K.…”

Section: Astrophysical Implications and Conclusionmentioning

confidence: 99%

Rotational spectra of interstellar N- and CN-PAHs: pyrene and coronene

Vats

Pathak

2022

Monthly Notices of the Royal Astronomical Society

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The detection of benzonitrile (C6H5CN), 1- and 2-cyano-naphthalene (C10H7CN) in the cold, dark molecular cloud TMC-1 at centimetre (cm) wavelengths has opened up prospects for the detection of other N- and CN-containing polycyclic aromatic hydrocarbons (PAHs). In this light, the pure rotational spectra of N-pyrene (C15H9N), CN-pyrene (C15H9CN), N-coronene (C23H11N) and CN-coronene (C23H11CN) are reported here for the first time. The B3LYP/6-311+G(d,p) level of theory, in the Density Functional Theory (DFT) calculations, achieves the best performance for calculating the spectroscopic parameters and simulating the rotational spectra. The large permanent dipole moment of CN-PAHs makes them the most suitable PAH species for detection in the interstellar medium. Additionally, pyrene’s smaller partition function makes CN-pyrene a prime candidate to be discovered in cold, dark molecular clouds such as the TMC-1. The present work sets a benchmark for theoretical rotational spectra of N- and CN-containing PAHs and may act as a guide for laboratory experiments and observational searches.

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“…Low frequency vibrational bands, like the ν 15 (OH torsion) fundamental of syn-VA investigated here, fall in the far-IR, where the advantage of using synchrotron generated radiation is most pronounced. 38 As such, a rapidly growing number of "complex" molecules (with low frequency torsional bands) have been investigated by far-IR synchrotron spectroscopy, including the OH containing chromophores, perchloric acid, 39 phenol, 40 formic acid, 41 acetone, 42 methanol, 43 glycolaldehyde, 44 and catechol, 45 and the CN containing chromophores, vinyl acetylene, 46 cyanoadamantane, 47 phenylpropiolonitrile, 48 ethyl cyanide, 49 aminoacetonitrile, 50 and benzonitrile, 51 the latter of which are particularly well suited for radioastronomy (on account of their very large dipole moments).…”

Section: Experimental Techniquementioning

confidence: 99%

Characterization of the Coriolis Coupled Far-Infrared Bands of syn-Vinyl Alcohol

Bunn

2022

J. Phys. Chem. A

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Rotational emission from vibrationally excited molecules are responsible for a large fraction of lines in the spectra of interstellar molecular clouds. Vinyl alcohol (VA) has two rotamers that differ in energy by 6.4 kJ/mol, both of which have been observed toward the molecular cloud, Sagittarius B2(N) [Turner and Apponi, Astrophys. J.2001561207]. Previously, we reported an analysis of the far-infrared spectrum of the higher energy rotamer, anti-VA [Bunn et al. Astrophys. J.201784767], yielding rotational and higher order distortion constants in the first excited vibrational state, and here, we report an analysis of the far-infrared spectrum of the lower energy rotamer, syn-VA, whose spectrum is significantly more complicated on account of Coriolis interactions that result in perturbations to the rovibrational spectrum. We account for those perturbations with the inclusion of Coriolis coupling constants in the fit, which couples the first excited OH torsional (ν15) and CCO bending (ν11) states. Inclusion of them resulted in more physically meaningful rotational and centrifugal distortion constants, and allows for accurate pure rotational line predictions to be made up to high energies. These will be particularly useful in searches for vibrationally excited syn-VA toward warm regions of interstellar molecular clouds, where we predict that it may be significantly abundant.

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A rotational and vibrational investigation of phenylpropiolonitrile (C6H5C3N)

Cited by 13 publications

References 34 publications

Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

Rotational spectra of interstellar N- and CN-PAHs: pyrene and coronene

Characterization of the Coriolis Coupled Far-Infrared Bands of syn-Vinyl Alcohol

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