title: Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes.
abstract: The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem.
authors.affiliation: Chemistry Department, Lomonosov Moscow State University, 119991 Moscow, Russia. Electronic address: lant@phys.chem.msu.ru.
authors.forename: Vadim A
authors.initials: VA
authors.lastname: Bataev
authors.affiliation: Chemistry Department, Lomonosov Moscow State University, 119991 Moscow, Russia.
authors.forename: Vladimir I
authors.initials: VI
authors.lastname: Pupyshev
authors.affiliation: Chemistry Department, Lomonosov Moscow State University, 119991 Moscow, Russia.
authors.forename: Igor A
authors.initials: IA
authors.lastname: Godunov
keywords: Anharmonic vibrations; Five-member heterocyclic aldehydes; Furfural; Internal rotation; Kinematic interaction