ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Theoretical Studies of SiC4H2 Isomers Delineate Three Low-Lying Silylidenes Are Missing in the Laboratory

Cite this: J. Phys. Chem. A 2020, 124, 5, 987–1002
Publication Date (Web):January 6, 2020
https://doi.org/10.1021/acs.jpca.9b11742
Copyright © 2020 American Chemical Society

    Article Views

    317

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Eleven isomers of SiC4H2 lying within 50 kcal mol–1 have been theoretically investigated using density functional theory and high-level coupled-cluster methods. Among them, four isomers, 1-ethynyl-3-silacycloprop-1(2)-en-3-ylidene (1), diethynylsilylidene (2), 1-sila-1,2,3,4-pentatetraenylidene (4), and 1,3-butadiynylsilylidene (5), have already been identified in the laboratory. The current investigation reports three low-lying (<1 eV) silylidenes [2-methylenesilabicyclo[1.1.0]but-1(3)-en-4-ylidene (3), 4-sila-2-methylenebicyclo[1.1.0]but-1(3)-en-4-ylidene (6), and 3-ethynyl-1-silapropadienylidene (7)] and three high-lying (>1 eV) silylidenes [2-sila-(didehydrovinylidene)cyclopropene (8), an isomer with a planar tetracoordinate carbon (ptC) atom (10), and 1-ethynyl-1-silapropadienylidene (11)], which remain elusive in the laboratory to date. Isomer 9 also contains a ptC atom, which turned out to be a transition state at all levels. Though all isomers are polar (μ ≠ 0), rotational spectrum is available only for 4. Using matrix isolation, three isomers (1, 2, and 5) have been trapped in the laboratory at 10 K. Considering the astrochemical relevance of silicon–carbide clusters in the interstellar medium, the current theoretical data demand new molecular spectroscopic studies on SiC4H2. Surprisingly, unlike the isovalent C5H2 isomers, where the bent carbenes are yet to be identified in the laboratory, the bent silylidenes (2 and 5) have been trapped in the case of SiC4H2. In both the cases, molecules with transannular C–C and/or Si–C bonds remain elusive, though they lie in the low-lying region. Using suitable precursors, whether these peculiar geometries (especially 3 and 6) would be identified or not in the laboratory needs to be addressed by molecular spectroscopists. The present investigation documents structural and spectroscopic information of SiC4H2 isomers, which may compliment future molecular spectroscopic observations including radioastronomical searches.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.9b11742.

    • Cartesian coordinates of the optimized geometries, total electronic energies, and zero-point vibrational energies (ZPVEs) calculated at different levels (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 20 publications.

    1. Nisha Job, Krishnan Thirumoorthy. Silicon Chemistry in the Interstellar Medium and Circumstellar Envelopes. ACS Earth and Space Chemistry 2024, 8 (3) , 467-482. https://doi.org/10.1021/acsearthspacechem.3c00284
    2. Nisha Job, Vijayanand Chandrasekaran, Venkatesan S. Thimmakondu, Krishnan Thirumoorthy. Theoretical Studies on the Isomerization Kinetics of Low-Lying Isomers of the SiC4H2 System. The Journal of Physical Chemistry A 2024, 128 (1) , 73-80. https://doi.org/10.1021/acs.jpca.3c05658
    3. Nisha Job, Krishnan Thirumoorthy. Chemical Bonding Perspective on Low-Lying SiC4H2 Isomers: Conceptual Quantum Chemical Views. The Journal of Physical Chemistry A 2022, 126 (50) , 9366-9374. https://doi.org/10.1021/acs.jpca.2c06230
    4. Sunanda Panda, Devipriya Sivadasan, Nisha Job, Aland Sinjari, Krishnan Thirumoorthy, Anakuthil Anoop, Venkatesan S. Thimmakondu. Why Are MgC3H Isomers Missing in the Interstellar Medium?. The Journal of Physical Chemistry A 2022, 126 (27) , 4465-4475. https://doi.org/10.1021/acs.jpca.2c02220
    5. Tarun Roy, Subhas Ghosal, Venkatesan S. Thimmakondu. Six Low-Lying Isomers of C11H8 Are Unidentified in the Laboratory–A Theoretical Study. The Journal of Physical Chemistry A 2021, 125 (20) , 4352-4364. https://doi.org/10.1021/acs.jpca.1c02247
    6. Aditya P. Pandey, Uday Kumar Padidela, Loganathan Konda Thulasiraman, Ramakrishnan Sethu, Pothiappan Vairaprakash, Venkatesan S. Thimmakondu. MgC6H2 Isomers: Potential Candidates for Laboratory and Radioastronomical Studies. The Journal of Physical Chemistry A 2020, 124 (37) , 7518-7525. https://doi.org/10.1021/acs.jpca.0c06401
    7. Soumadip Banerjee, Avik Ghosh, Suniti Ghosh, Ria Sinha Roy, Tamalika Ash, Tanay Debnath, Abhijit K. Das. Thermodynamics and spectroscopic properties of C2H5CONH2 found in Sagittarius B2(N1). Computational and Theoretical Chemistry 2023, 1226 , 114184. https://doi.org/10.1016/j.comptc.2023.114184
    8. Otilia Mó, Ibon Alkorta, Jean-Claude Guillemin, Manuel Yáñez. Dramatic effect of the nature of R on the intrinsic acidity and basicity of potential astrochemical R–C≡COH and R–C≡CSH compounds. Theoretical Chemistry Accounts 2023, 142 (3) https://doi.org/10.1007/s00214-023-02967-0
    9. Prasenjit Das, Maya Khatun, Anakuthil Anoop, Pratim Kumar Chattaraj. CSi n Ge 4 −n 2+ ( n = 1–3): prospective systems containing planar tetracoordinate carbon (ptC). Physical Chemistry Chemical Physics 2022, 24 (27) , 16701-16711. https://doi.org/10.1039/D2CP01494G
    10. Avik Ghosh, Soumadip Banerjee, Subhendu Sarkar, Tanay Debnath, Tamalika Ash, Ria Sinha Roy, Abhijit K. Das. Energetics and Spectroscopic Properties of Low‐lying CaC 6 H 2 Isomers: An Astrochemical Perspective. ChemistrySelect 2022, 7 (22) https://doi.org/10.1002/slct.202200763
    11. Venkatesan S. Thimmakondu, Aland Sinjari, Diego Inostroza, Pothiappan Vairaprakash, Krishnan Thirumoorthy, Saikat Roy, Anakuthil Anoop, William Tiznado. Why an integrated approach between search algorithms and chemical intuition is necessary?. Physical Chemistry Chemical Physics 2022, 24 (19) , 11680-11686. https://doi.org/10.1039/D2CP00315E
    12. Prasenjit Das, Pratim Kumar Chattaraj. CSiGaAl 2 −/0 and CGeGaAl 2 −/0 having planar tetracoordinate carbon atoms in their global minimum energy structures. Journal of Computational Chemistry 2022, 43 (13) , 894-905. https://doi.org/10.1002/jcc.26845
    13. Maya Khatun, Saikat Roy, Sandip Giri, Sasanka Sankhar Reddy CH, Anakuthil Anoop, Venkatesan S. Thimmakondu. BAl4Mg−/0/+: Global Minima with a Planar Tetracoordinate or Hypercoordinate Boron Atom. Atoms 2021, 9 (4) , 89. https://doi.org/10.3390/atoms9040089
    14. Prasenjit Das, Pratim Kumar Chattaraj. In Silico Studies on Selected Neutral Molecules, CGa2Ge2, CAlGaGe2, and CSiGa2Ge Containing Planar Tetracoordinate Carbon. Atoms 2021, 9 (3) , 65. https://doi.org/10.3390/atoms9030065
    15. Nisha Job, Maya Khatun, Krishnan Thirumoorthy, Sasanka Sankhar Reddy CH, Vijayanand Chandrasekaran, Anakuthil Anoop, Venkatesan S. Thimmakondu. CAl4Mg0/−: Global Minima with a Planar Tetracoordinate Carbon Atom. Atoms 2021, 9 (2) , 24. https://doi.org/10.3390/atoms9020024
    16. Krishnan Thirumoorthy, Vijayanand Chandrasekaran, Andrew L. Cooksy, Venkatesan S. Thimmakondu. Kinetic Stability of Si2C5H2 Isomer with a Planar Tetracoordinate Carbon Atom. Chemistry 2021, 3 (1) , 13-27. https://doi.org/10.3390/chemistry3010002
    17. Zhenghai Yang, Srinivas Doddipatla, Ralf I. Kaiser, Anatoliy A. Nikolayev, Valeriy N. Azyazov, Alexander M. Mebel. On the Synthesis of the Astronomically Elusive 1-Ethynyl-3-Silacyclopropenylidene (c-SiC 4 H 2 ) Molecule in Circumstellar Envelopes of Carbon-rich Asymptotic Giant Branch Stars and Its Potential Role in the Formation of the Silicon Tetracarbide Chain (SiC 4 ). The Astrophysical Journal Letters 2021, 908 (2) , L40. https://doi.org/10.3847/2041-8213/abde36
    18. Venkatesan S. Thimmakondu. MgC2H2 isomers – simple penta-atomic molecules missing in the laboratory. Chemical Physics 2020, 538 , 110899. https://doi.org/10.1016/j.chemphys.2020.110899
    19. Shampa Raghunathan, Komal Yadav, V. C. Rojisha, Tanashree Jaganade, V. Prathyusha, Swetha Bikkina, Upakarasamy Lourderaj, U. Deva Priyakumar. Transition between [ R ]- and [ S ]-stereoisomers without bond breaking. Physical Chemistry Chemical Physics 2020, 22 (26) , 14983-14991. https://doi.org/10.1039/D0CP02918A
    20. Krishnan Thirumoorthy, Andrew L. Cooksy, Venkatesan S. Thimmakondu. Si 2 C 5 H 2 isomers – search algorithms versus chemical intuition. Physical Chemistry Chemical Physics 2020, 22 (10) , 5865-5872. https://doi.org/10.1039/C9CP06145B

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect