Discrete variable approaches to tetratomic molecules: part II: application to H2O2 and H2CO.
We have carried out large-scale calculations for accurate vibrational energy levels of formaldehyde and hydrogen peroxide. The discrete variable representations of the radial and angular coordinates are employed together with the contraction scheme resulting from several diagonalization/truncation steps. The global potential energy surface due to Carter et al. [J. Mol. Spectrosc. 90 (1997) 729] is used for H2CO and due to Koput et al. [J. Phys. Chem. A 102 (1998) 6325] for H2O2. For both molecules, the calculated vibrational energy levels are characterized by combining vibrationally averaged geometries and expectation values of rotational constants with several adiabatic projection schemes for automatic quantum number assignments. The energy levels of H2CO involving the excited v2 and v3 vibrations appear as resonances beyond the zero-order picture consisting of uncoupled 3D stretching and 2D bending modes. The torsional energy levels of H2O2 are studied in great detail and different energy patterns occurring below and above the cis barrier are discussed. Our full dimensional calculations for H2O2 have shown that the OH triad levels, 2vOH, are symmetry adapted local mode states.
Mladenović
Mirjana
M
Institut für Physikalische Chemie, Universität Göttingen, Germany. mmladen@gwdg.de
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005557:Formaldehyde / Q000032:analysis / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000032:analysis / Q000737:chemistry*; D008962:Models, Theoretical; D013055:Spectrophotometry, Infrared / Q000379:methods*; D014732:Vibration
D005557:Formaldehyde; D006861:Hydrogen Peroxide