- International Centre for Quantum and Molecular Structures, Department of Physics, College of Sciences, Shanghai University, Shanghai, China
The James Webb Space Telescope (JWST) opened a new era for the identification of molecular systems in the interstellar medium (ISM) by vibrational features. One group of molecules of increasing interest is cyano-derivatives of aromatic organic molecules, which have already been identified in the ISM on the basis of the analysis of rotational signatures, and so, are plausible candidates for the detection by the JWST. Benzonitrile considered in this work represents a suitable example for the validation of a computational strategy, which can be further applied for different, larger, and not-yet observed molecules. For this purpose, anharmonic simulations of infrared (IR) spectra have been compared with recent FTIR experimental studies. The anharmonic computations using the generalized second-order vibrational perturbation theory (GVPT2) in conjunction with a hybrid force field combining the harmonic part of revDSD-PBEP86-D3/jun-cc-pVTZ with anharmonic corrections from B3LYP-D3/SNSD show very good agreement with those in the experiment, with a mean error of
1 Introduction
Despite being initially considered too harsh and diluted for molecule creation and survival, it is now recognized that several chemical processes can happen in astronomic environments leading to more than 310 molecules already detected in the interstellar medium (ISM) or circumstellar shells (Endres et al., 2016). Several of these molecules have been detected in the last decade, in particular, a number of complex organic species (COMs), defined as astrophysically relevant organic molecules consisting of six or more atoms. Some COMs that contain C, H, N, O, and possibly also S atoms can be claimed as prebiotic (Fulvio et al., 2021). To date, more than 30 prebiotic molecules have been detected in Taurus molecular cloud 1 (TMC-1), a dust-enshrouded gaseous cloud located 400 light-years from the Sun in the Taurus constellation. Such progress and fast increase in new detections has become possible due to advances in instrumentation, in particular the sub-millimeter and radio domains, allowing the analysis of the lowest rotational lines where radiation can pass through dust-enshrouded clouds (Guélin and Cernicharo, 2022).
However, rotational transitions are not always suitable and accessible for a study, for instance, for exoplanet atmospheres or dense dark regions, for which vibrational spectroscopies are often the methods of choice. The increasing importance of vibrational transitions in astrochemical context is clearly represented by the James Webb Space Telescope (JWST), which, with the infrared (IR) (Frost et al., 2022) observations obtained by the mid-infrared (MIR) and near-IR (NIR) instruments integrated within the Integrated Science Instrument Module (ISIM, Near-Infrared Camera [NIRCam], Near-Infrared Spectrograph [NIRSpec], Mid-Infrared Instrument [MIRI], and Jet Propulsion Laboratory [JPL]), already provides superlative sensitivity, spectral resolution, and wavelength coverage compared to previous space telescopes, such as Herschel, that observe in the visible and ultraviolet spectra (see Figure 1). These emerging experimental data already provide new information about the major ices in molecular cloud cores just prior to their collapse to form protostars (McClure et al., 2023). Currently, the Mars 2020 Perseverance rover also searches for signs of organic matter, in the contexts of the emergence of life, as well as its consideration as a habitable planet, performing, among others, NIR studies using SuperCam (Perez et al., 2017; Eigenbrode et al., 2018; Lasne, 2021; Sharma et al., 2023; McIntosh et al., 2024). These missions yield a huge amount of new significant results, which need to be analyzed, also highlighting the urgent need for accurate reference data in the MIR-to-NIR (0.6–28
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Figure 1. Cyano-derivatives in the ISM and the year of detection by rotational (left panel) or vibrational (right panel) features. Left panel: astro- COMs and Herschel’s view of TMC-1 (Herschel Space Observatory, 2017) (credit: ESA/Herschel/NASA/JPL-Caltech TMC-1). Right panel:
Spectroscopic techniques are the key for the analysis of astronomical observations and the detection of molecules in the interstellar medium and other astrochemical environments, such as atmospheres or soils of exoplanets or planetary moons (Loru et al., 2022; Lemmens et al., 2022; Mackie et al., 2022; Peeters et al., 2021; K. Lemmens et al., 2023; Petrignani and Candian, 2022; Puzzarini et al., 2023). However, the investigation of the chemical composition of “astrochemical samples” is complicated due to the concomitant presence of many, possibly unknown species. The detection of molecules is based on the comparison of spectra from spectroscopic observations in space with reference experiments from the laboratory (Puzzarini et al., 2023). Unfortunately, the latter might be limited, incomplete, or difficult to obtain under appropriate conditions (Barone et al., 2015c; Fortenberry, 2024b). The optimal strategy is represented by the combination of experiments with the theoretical approaches (Barone et al., 2021; Puzzarini, 2022), supporting and/or complementing laboratory studies (Biczysko et al., 2018a; Barone and Puzzarini, 2023; Fortenberry, 2024a). An increasing role of computational spectroscopy is related to its increasing accuracy (Yang et al., 2021; Barone and Puzzarini, 2023), as well as the possibility to match different, often extreme environmental conditions possible in space (Barone et al., 2015c; Biczysko et al., 2018b; Zapata Trujillo et al., 2023; Fortenberry, 2024b).
Among all the molecules detected to date in the ISM, over 30% bear a nitrogen atom, which usually bonds to carbon, in a large fraction (over 80% of species) by the triple C
In this work, we focus on the first observed cyano-astroCOM, i.e., benzonitrile (McGuire et al., 2018). The experimental microwave spectrum of benzonitrile was first studied simultaneously by Erlandsson (1954) and Lide (1954). Bak et al. conducted comprehensive analyses of benzonitrile utilizing infrared and centimeter-wave techniques, also including feasible mono-substituted isotopologs (Bak and Nielsen, 1960; Bak et al., 1962). This led to the first derivation of a substitution structure,
This work focuses on the IR spectra in the MIR-NIR region, first comparing the simulated infrared spectra with the available experimental counterparts and then providing the prediction of not yet available spectral data, which can support either laboratory or astrochemical studies.
2 Computational details
In order to simulate the spectroscopic parameters of benzonitrile in its electronic ground state
Computations of the third- and fourth-order derivatives of the potential energy surface have been performed at the B3LYP level by the numerical differentiation (Barone, 2005; Bloino, 2015) of analytic second-order derivatives, while the cubic electric dipole moment surfaces have been obtained through numerical differentiations of the dipole moment derivatives. The revDSD equilibrium and harmonic computations have been combined with B3LYP anharmonic computations to create a hybrid model used in spectroscopic simulations. The consistency of these two sets of data has been checked automatically, as implemented in GAUSSIAN 16. In other words, the overlap between two sets of normal modes (two different levels of theory) is defined using the linear transformation, as proposed by Duschinsky (1937):
where
This cost-effective (Xu et al., 2024) hybrid revDSD/B3LYP scheme has been further used to compute spectroscopic parameters using the second-order vibrational perturbation theory (VPT2) (Nielsen, 1951; Mills, 1972). The ground vibrational state rotational constants have been obtained from the revDSD equilibrium structure by adding vibrational corrections computed at the revDSD/B3LYP level, which also provided data allowing the determination of the quartic and sextic centrifugal-distortion constants (Puzzarini et al., 2010; Puzzarini, 2013). For the vibrational spectra, it is also necessary to account for the possible presence of anharmonic resonances (Amos et al., 1991; Martin et al., 1995; Barone, 2005; Vázquez and Stanton, 2007; Rosnik and Polik, 2014; Barone et al., 2014; Bloino et al., 2015; Bloino, 2015; Krasnoshchekov et al., 2015; Franke et al., 2021; Mendolicchio et al., 2021; Franke et al., 2021) by the generalized VPT2 (GVPT2) model (Bloino and Barone, 2012; Bloino et al., 2015), where nearly resonant contributions are removed from the perturbative treatment (leading to the deperturbed model, DVPT2) and treated in a second step variationally. Resonance definition and general recommendations on the applied computational procedures are described in detail in the tutorial review by Bloino et al. (2016). It should be noted that, although improved criteria to define automatic resonances have been proposed recently, they would have negligible impacts on the energies (Yang and Bloino, 2022). Overall, the GVPT2 scheme employed in this work has been successfully applied to medium-sized or larger biomolecules with up to 100 atoms (Fornaro et al., 2015; Fusè et al., 2019; Yatsyna et al., 2019; Green and Improta, 2020; Yang et al., 2021; Sheng et al., 2021), also in the astrochemical context (Zhao et al., 2021; McIntosh et al., 2024; Alberini et al., 2024), so it is a valuable tool to be employed also for significantly larger cyano-astroCOMs.
3 Results and discussion
3.1 Equilibrium structure and rotational parameters
Selected equilibrium structural parameters of benzonitrile calculated at the revDSD/junTZ level are shown in Figure 2, while Table 1 compares all equilibrium parameters with the semi-experimental equilibrium structure
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Figure 2. Structural parameter of benzonitrile as computed at the rDSD/junTZ level, with bond lengths (black) in Å and angles (blue) in degrees.
The final validation is provided by the direct comparison with the experiment, i.e., spectroscopic constants from Watson’s asymmetric rotor Hamiltonian (A-reduction,
3.2 Vibrational properties and IR spectra
Table 3 compares harmonic vibrational wavenumbers and IR intensities with those computed at the CCSD(T)/ANO1 level, showing very good agreement with the average error of approximately 6
Table 4 lists all fundamental anharmonic wavenumbers and IR intensities of benzonitrile computed at the rDSD/junTZ//B3PLYP/SNSD GVPT2 level, while selected overtones and combination bands are given in Table 5. The accuracy of the simulated IR spectra of benzonitrile in the 500
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Table 4. Fundamental wavenumbers
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Table 5. Non-fundamental band wavenumbers
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Figure 3. IR spectrum of benzonitrile in the range 500–4,000
A direct comparison between the spectra given in Figure 3 highlights that the GVPT2 computation not only correctly predicts fundamental bands but also a pattern of five distinct non-fundamental bands in the
Overall, the good accuracy of our simulations, for both fundamental and non-fundamental transitions, allows us to predict the spectra in the NIR region, which is shown in Figures 4A and B for
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Figure 4. NIR spectra simulated at the GVPT2//rDSD/junTZ//B3LYP/SNSD level. The spectra were broadened by Lorentzian functions with HWHM of 2
4 Conclusion and astrochemical implications
Good accuracy of simulated MIR spectra, confirmed by a comparison with available experimental results, allowed us to provide predictions regarding the “missing” data on relevance for the astrochemical observations, in particular, concerning the NIR region.
The availability of NIR references is important for the interpretation of data collected during the Mars 2020 (Williford et al., 2018) space mission by instruments such as SuperCam, for incoming ExoMars 2022 (ESZ-Roscosmos) (Vago et al., 2017), as well as for the JWST observations by the NIRSpec (McClure et al., 2023). The advantage of NIR is its lower spectrum congestion than MIR, which is also clearly visible in Figures 3, 4. However, these reference NIR data are often very scarce and were not available even for benzonitrile prior to this work. It has been already highlighted that anharmonic computations provide significant support in the analysis of experimental results and identification of plausible molecules by NIR features (Fornaro et al., 2020; Alberini et al., 2024).
Computational spectroscopy can also support the identification of B
Extensive laboratory experimental investigation of the photoabsorption spectra of benzonitrile recorded using synchrotron radiation in
The most relevant are those based on aromatic systems, such as 1- and 2-cyanocyclopentadiene (McCarthy et al., 2021; Lee et al., 2021), and 1- and 2-cyanonaphthalene (McGuire et al., 2021), which have been already discovered in TMC-1. However, it can be expected that similar accuracy can also be obtained for aliphatic systems, for which several conformers can be present (Barone et al., 2013; 2015b). This situation was highlighted by the recent discovery of five cyano-derivatives of propene (
Data availability statement
The original contributions presented in the study are included in the article/Supplementary Material; further inquiries can be directed to the corresponding author.
Author contributions
YX: formal analysis, investigation, validation, writing–original draft, writing–review and editing, data curation, and visualization. MB: formal analysis, investigation, validation, writing–original draft, writing–review and editing, conceptualization, funding acquisition, methodology, project administration, resources, and supervision.
Funding
The author(s) declare that financial support was received for the research, authorship, and/or publication of this article. This work was performed within COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology). This work was supported by the National Natural Science Foundation of China (Grant No. 31870738).
Acknowledgments
MB acknowledges support from the COST Action “COSY,” in particular, discussions with Action Chair Prof. María Pilar de Lara-Castells, Action Vice-Chair Prof. Cristina Puzzarini, and WG5 “Confined Systems in Astrochemistry” Leader Prof. Lauri Halonen. MB and XY thank Prof. Julien Bloino for fruitful discussions on anharmonic computations.
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision.
Publisher’s note
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Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fchem.2024.1439194/full#supplementary-material
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Keywords: vibrational spectra, density functional theory, second-order vibrational perturbation theory, near-infrared, James Webb Space Telescope
Citation: Xu Y and Biczysko M (2024) Toward the identification of cyano-astroCOMs via vibrational features: benzonitrile as a test case. Front. Chem. 12:1439194. doi: 10.3389/fchem.2024.1439194
Received: 27 May 2024; Accepted: 12 August 2024;
Published: 03 September 2024.
Edited by:
Jean-Claude Guillemin, UMR6226 Institut des Sciences Chimiques de Rennes (ISCR), FranceReviewed by:
Barbara Michela Giuliano, Max Planck Institute for Extraterrestrial Physics, GermanyNicola Tasinato, Normal School of Pisa, Italy
Copyright © 2024 Xu and Biczysko. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
*Correspondence: Malgorzata Biczysko, malgo.biczysko@gmail.com