Rovibrational spectra of diatomic molecules in strong electric fields: The adiabatic regime
- Theoretische Chemie, Physikalisch-Chemisches Institut, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany)
We investigate the effects of a strong electric field on the rovibrational spectra of diatomic heteronuclear molecules in a {sup 1}{sigma}{sup +} electronic ground state. Using a hybrid computational technique combining discretization and basis set methods, the full rovibrational equation of motion is solved. As a specific example, the rovibrational spectrum and properties of the carbon monoxide molecule are analyzed for experimentally accessible field strengths. Results for energy levels, expectation values, and rovibrational spectral transitions are presented. They indicate that, while low-lying states are not significantly affected by the field, for highly excited states strong orientation and hybridization are achieved. We propose an effective rotor Hamiltonian, including the main properties of each vibrational state, to describe the influence of an electric field on the rovibrational spectra of a molecular system with a small coupling between its rotational and vibrational motions. The validity of this approach is illustrated by comparison with the results obtained with the fully coupled rovibrational Schroedinger equation. We thereby demonstrate that it is possible to create state-dependent hybridization of a molecular system, which is of importance for vibrational state-selective chemical reactions. This state dependence is individually different for each molecular system and represents therefore a characteristic feature of the species.
- OSTI ID:
- 20640747
- Journal Information:
- Physical Review. A, Vol. 69, Issue 2; Other Information: DOI: 10.1103/PhysRevA.69.023402; (c) 2004 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA); ISSN 1050-2947
- Country of Publication:
- United States
- Language:
- English
Similar Records
H{sub 2}{sup +}, HeH and H{sub 2}: Approximating potential curves, calculating rovibrational states
Dressed-bound-state molecular strong-field approximation: Application to above-threshold ionization of heteronuclear diatomic molecules