|Recent publications on molecular symmetry  |
The Formation of Fourfold Rovibrational Energy Level Clusters in Triatomic Molecules
The energy level structure of a rigidly rotating H2130Te molecule. The term values are plotted relative to the highest term value for each J multiplet.
The rotational energy level structure in the vibrational ground state of the H2130Te molecule, calculated directly from the potential energy function of the molecule. The term values are plotted relative to the highest term value for each J multiplet. The calculated spacings are in good agreement with values derived from experiment.
Comparison of the two figures shows that when we allow the molecule to vibrate, its rotational energy structure changes drastically at high J: four-fold energy clusters are formed.
Recent Publications on Four-fold Energy Clusters
Per Jensen, G. Osmann, and I. N. Kozin: The Formation of Four-fold Rovibrational Energy Clusters in H2S, H2Se, and H2Te, in: "Advanced Series in Physical Chemistry", vol. 9, "Vibration-Rotational Spectroscopy and Molecular Dynamics" (D. Papousek, Ed., ISBN 981-02-1635-1), pp. 298-351, World Scientific Publishing Company, Singapore, 1997.
(99) P. C. Gomez, L. F. Pacios, and Per Jensen: Fourfold Clusters of Rovibrational Energies in H2Po Studied with an ab initio Potential Energy Function, J. Mol. Spectrosc. 186, 99 (1997).
(98) P. C. Gomez and Per Jensen: A Potential Energy Surface for the Electronic Ground State of H2Te Derived from Experiment, J. Mol. Spectrosc. 185, 282 (1997).
The Renner Effect
The effect on the spectrum of electronic orbital and spin angular momentum
in triatomic molecules is being investigated in collaboration with P. R. Bunker,
W. P. Kraemer (Max Planck Institute of Astrophysics, Garching, Germany),
R. J. Buenker (University of Wuppertal) and others.
This is generally
termed the Renner effect. We have developed a computer program with which we
can calculate both the positions and intensities of the lines
in a spectrum that arise from transitions between the two halves of a
Renner state. Applications to free radicals and molecular ions are being
undertaken using potential energy surfaces calculated by ab initio methods.
We have predicted the electronic
spectra of the NH2+ and CH2+ ions, and these predictions will be of
assistance in their search. |
For CH2+ it has been conjectured, on the basis of the interpretation of data obtained using the Coulomb explosion imaging (CEI) method, that there is a large nonadiabatic contribution to the low-lying wavefunctions beyond that coming from the Renner effect. Very recently, we have calculated the energies of the lowest excited electronic states and find, in agreement with results already in the literature, that the excited electronic states of CH2+ are at much too high an energy (greater than 6 eV) for such nonadiabatic interaction to be significant. To compare with the CEI results we calculate the Boltzmann averaged bending angle distribution using our previously calculated ab initio potential energy curves of the X,A pair of Renner interacting potentials, and make full allowance for the Renner effect in the calculation of the wavefunctions. This ab initio calculation leads to a distribution that is significant over a narrower range of bending angles than that obtained experimentally by the CEI method. Depending on the accuracy of the CEI distribution this could indicate an error in the ab initio potential energy surfaces. We have modified the shape of the X-state surface in order to approximately reproduce the CEI result, and the change we have to make is rather large. An experimental determination of some of the bending energy level separations for CH2+ would be a more definitive way of testing the shape of the potential surface.
The CH2 and HO2 molecules are subjects of further calculations.
Recent Publications on the Renner Effect
(108) G. Osmann, P. R. Bunker, W. P. Kraemer, and Per Jensen: Coulomb Explosion Imaging and the CH2+ Molecule, Chem. Phys. Lett., 309, 299-306 (1999).
(105) G. Osmann, P. R. Bunker, Per Jensen, R. J. Buenker, J.-P. Gu, and G. Hirsch: A Theoretical Investigation of the Renner Interactions and Magnetic Dipole Transitions in the A - X Electronic Band System of HO2, J. Mol. Spectrosc., 197, 262-274 (1999).
(103) J.-P. Gu, G. Hirsch, R. J. Buenker, M. Brumm, G. Osmann, P. R. Bunker and P. Jensen: A theoretical study of the absorption spectrum of singlet CH2, J. Mol. Struct., in press.
(101) G. Osmann, P. R. Bunker, P. Jensen and W. P. Kraemer: An Ab Initio Study of the NH2+ Absorption Spectrum. J. Mol. Spectrosc. 186, 319 (1997)
(100) G. Osmann, P. R. Bunker, P. Jensen and W. P. Kraemer: A Theoretical Calculation of the Absorption Spectrum of CH2+. Chem. Phys. 225, 33 (1997).
(85) J.-P. Gu, R. J. Buenker, G. Hirsch, P. Jensen and P. R. Bunker: An ab initio calculation of the BH2- rovibronic energies: a very small singlet-triplet splitting. J. Mol. Spectrosc. 178, 172 (1996).
(79) M. Kolbuszewski, P. R. Bunker, W. P. Kraemer, G. Osmann and P. Jensen: An ab initio calculation of the rovibronic energies of the BH2 molecule. Mol. Phys. 88, 105 (1996).
We have implemented the stabilization method of Mandelshtam, Taylor and co-workers
to calculate the quasibound states of a triatomic molecule.
So far, the resulting computer program has been applied to
1B2 ozone and to
H2O++ in its electronic ground state.
Recent Publications on Quasibound States
(106) P. R. Bunker, O. Bludský, Per Jensen, S. S. Wesolowski, T. J. Van Huis, Y. Yamaguchi, and H. F. Schaefer III: The H2O++ Ground State Potential Energy Surface, J. Mol. Spectrosc., in press.
(95) O. Bludský and Per Jensen:
The Calculation of the Bound and Quasibound Vibrational States
of Ozone in its 1B2 Electronic State,
Mol. Phys. 91, 653 (1997).