Photorotamerization of matrix-isolated acrylic acid revisited
Özet
In this study, the conformational preferences and photochemistry of acrylic acid (AA, CH(2)=CHCOOH) monomer isolated in cryogenic argon and krypton matrices were interpreted, based on results of quantum chemical calculations. Natural bond orbital analysis allowed to shed light on the main electronic effects determining the relative stability of the conformers of the molecule in the ground electronic state. The conformational isomerization taking place upon UV-irradiation of the matrix-isolated compound (lambda similar to 243 nm) was explained, based on theoretical complete active space self-consistent field/complete active space with second order perturbation theory (CASSCF/CASPT2) and time-dependent density functional theory (TD-DFT) results, allowing to rationalize the nearly equal populations of the two lowest energy conformers of the molecule observed in the photostationary state. Besides, details of the infrared spectra of the compound were reinterpreted based on the calculated spectra for the two most stable conformers of the molecule. In particular, the assignments for the out-of-plane A '' symmetry vibrations were revised
Kaynak
Journal of Chemical PhysicsCilt
134Sayı
15Koleksiyonlar
- Makale Koleksiyonu [1058]
- PubMed İndeksli Yayınlar Koleksiyonu [1498]
- Scopus İndeksli Yayınlar Koleksiyonu [8325]
- WoS İndeksli Yayınlar Koleksiyonu [7605]