1. Matrix Isolation Infrared Spectra and Photochemistry of Hydantoin
- Author
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Cláudio M. Nunes, Gulce Ogruc Ildiz, Rui Fausto, and Fen Edebiyat Fakültesi / Faculty of Letters and Sciences Fizik / Physics
- Subjects
Models, Molecular ,Türevler ,Ultraviolet Rays ,Infrared ,Molecular Conformation ,Infrared spectroscopy ,Density ,Electronic structure ,Imidazolidines ,Photochemistry ,Phase Transition ,Kristal Yapıları ,Crystal-Structures ,Spectroscopy, Fourier Transform Infrared ,Physics::Atomic and Molecular Clusters ,Physical and Theoretical Chemistry ,Physics::Chemical Physics ,Cambridge Yapısal Veri Tabanı ,Cambridge Structural Database ,Mp2 energy ,Spectroscopy ,Mp2 Enerjisi ,Röntgen ,Valence (chemistry) ,Chemistry ,Hydantoins ,Matrix isolation ,Spektroskopi ,Hydrogen Bonding ,Stereoisomerism ,Photochemical Processes ,Vibrational-Spectra ,Potential energy ,Hidrojen ,Models, Chemical ,Ab Initio ,x-ray ,Quantum Theory ,Thermodynamics ,Anticonvulsants ,Yoğunluk ,Electron configuration ,Crystallization ,Derivatives ,Titreşim-Spektrumları ,Natural bond orbital ,Hydrogen - Abstract
Hydantoin (C(3)H(4)N(2)O(2), 2,4-imidazolidinedione) was isolated in argon matrix at 10 K and its infrared spectrum and unimolecular photochemistry were investigated. The molecular structure of the compound was studied both at the DFT(B3LYP) and MP2 levels of approximation with valence triple- and quadruple-ζ basis sets (6-311++G(d,p); cc-pVQZ). It was concluded that the minima in the potential energy surfaces of the molecule correspond to C(1) symmetry structures. However, the energy barrier separating the two-equivalent-by-symmetry minima stays below their zero-point energy, which makes the C(s) symmetry structure, which separates the two minima, the experimentally relevant one. The electronic structure of the molecule was studied in detail by performing the Natural Bond Orbital analysis of its electronic configuration within the DFT(B3LYP)/cc-pVQZ space. The infrared spectrum of the matrix isolated compound was fully assigned also with help of the theoretically predicted spectrum. Upon irradiation at λ = 230 nm, matrix-isolated hydantoin was found to photofragment into isocyanic acid, CO, and methylenimine.
- Published
- 2013
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