These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: The all-Cartesian reaction plane Hamiltonian: formulation and application to the H-atom transfer in tropolone.
    Author: Giese K, Kühn O.
    Journal: J Chem Phys; 2005 Aug 01; 123(5):054315. PubMed ID: 16108647.
    Abstract:
    In this work we present an all-Cartesian reaction surface approach, where the large amplitude coordinates span the so-called reaction plane, that is, the unique plane defined by the two minima and the saddle-point structure of an isomerization reaction. Orthogonal modes are treated within harmonic approximation which gives the total Hamiltonian an almost separable form that is suitable for multidimensional quantum dynamics calculations. The reaction plane Hamiltonian is constructed for the H-atom transfer in tropolone as an example for a system with an intramolecular O...H-O hydrogen bond. We find ground-state tunneling splittings of 3.5 and 0.16 cm(-1) for the normal and deuterated species, respectively. We calculated infrared-absorption spectra for a four-dimensional model focusing on the low-frequency region. Here, we identify a reaction mode which is closely connected to the tautomerization that is reflected in the increase of tunneling splitting to 18 cm(-1) upon excitation.
    [Abstract] [Full Text] [Related] [New Search]