Rovibrational spectra of diatomic molecules in strong electric fields: The adiabatic regime

Journal Article · Sun Feb 01 04:00:00 EST 2004 · Physical Review. A

DOI:https://doi.org/10.1103/PhysRevA.69.023402· OSTI ID:20640747

Gonzalez-Ferez, R ^[1]; Schmelcher, P ^[1]

---

1. 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, Journal Name: Physical Review. A Journal Issue: 2 Vol. 69; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
CARBON MONOXIDE
COMPARATIVE EVALUATIONS
COUPLING
ELECTRIC FIELDS
ELECTRO-OPTICAL EFFECTS
EQUATIONS OF MOTION
GROUND STATES
HAMILTONIANS
MOLECULES
ORIENTATION
POTENTIAL ENERGY
SCHROEDINGER EQUATION
SURFACES
VIBRATIONAL STATES