Recent studies postulate that the presence of polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM) could have been formed through resonance-stabilized arylcarbene intermediates. However, identifying most of these reactive intermediates is very challenging experimentally due to their metastability and other experimental constrains. Thus, computational studies that cover the thermodynamic versus kinetic stability of various possible structures would be beneficial for successfully identifying new molecules either in the laboratory and/or in the ISM. In this paper, more than four hundred C11H8 carbene isomers have been theoretically investigated employing density functional theory (DFT). Hybrid density functionals B3LYP and ωB97XD with 6-311 + G (d,p) basis set have been used for singlet electronic states, whereas, triplet spin states were optimized at the same level using an unrestricted Hartree-Fock wavefunction. Although the skeletal structures of C11H8 can be categorized into monocyclic, bicyclic, tricyclic, tetracyclic and acyclic isomers, bicyclic carbenes have shown better stability due to the presence of resonance stabilized azulenyl/naphthyl rings. In this category, some isomers (1-, 2-, 5- and 6-azulenylcarbenes and 1- and 2-naphthylcarbenes) have also been detected recently in the laboratory and simple aromatic carbenes such as cyclopropenylidene and its homologues are detected in the ISM. Thus, we have systematically investigated the energetic and spectroscopic properties of resonance stabilized 5-, 6-, 7- and 8-membered ring containing bicyclic isomers of C11H8 and the fingerprint regions of the infrared spectrum for each class of these bicyclic compounds.
We have theoretically investigated nine unusual isomers of the molecular formula C5H4 using coupled cluster (CC) and density functional theory (DFT) methods. These molecules possess non-classical structures consisting of two pyramidanes, three planar tetracoordinate carbon (ptC), and four spiro types of isomers. Both the pyramidanes (tetracyclo-[2.1.0.01,3.02,5]pentane; py-1 and tricyclo-[2.1.0.02,5]pentan-3-ylidene; py-2) are minima on the potential energy surface (PES) of C5H4. Among the three isomers containing ptC, (SP4)-spiro [2.2]pent-1-yne (ptC-2) is a minimum, whereas isomer, (SP4)-spiro [2.2]pent-1,4-diene (ptC-1) is a fourth-order saddle point, and (SP4)-sprio[2.2]pent-1,4-diylidene (ptC-3) is a transition state. The corresponding spiro isomers spiro[2.2]pent-1,4-diene (spiro-1), sprio[2.2]pent-1,4-diylidene (spiro-3) and spiro[2.2]pent-4-en-1-ylidene (spiro-4) are local minima, except spiro[2.2]pent-1-yne (spiro-2), which is a second-order saddle point. All relative energies are calculated with respect to the global minimum (pent-1,3-diyne; 1) at the CCSD(T)/cc-pVTZ level of theory. Quantum chemical calculations have been performed to analyze the bonding and topological configurations for all these nine isomers at the B3LYP/6-311+G(d,p) level of theory for a better understanding of their corresponding electronic structures. ptC-2 was found to be thermodynamically more stable than its corresponding spiro counterpart (spiro-2) and possesses a high dipole moment (μ = 4.64 D). The stability of the ptC structures with their higher spin states has been discussed.
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