Classical and quantum mechanics of diatomic molecules in tilted fields.
We investigate the classical and quantum mechanics of diatomic molecules in noncollinear (tilted) static electric and nonresonant linearly polarized laser fields. The classical diatomic in tilted fields is a nonintegrable system, and we study the phase space structure for physically relevant parameter regimes for the molecule KCl. While exhibiting low-energy (pendular) and high-energy (free-rotor) integrable limits, the rotor in tilted fields shows chaotic dynamics at intermediate energies, and the degree of classical chaos can be tuned by changing the tilt angle. We examine the quantum mechanics of rotors in tilted fields. Energy-level correlation diagrams are computed, and the presence of avoided crossings quantified by the study of nearest-neighbor spacing distributions as a function of energy and tilting angle. Finally, we examine the influence of classical periodic orbits on rotor wave functions. Many wave functions in the tilted field case are found to be highly nonseparable in spherical polar coordinates. Localization of wave functions in the vicinity of classical periodic orbits, both stable and unstable, is observed for many states.
Arango
Carlos A
CA
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
Kennerly
William W
WW
Ezra
Gregory S
GS
D000465:Algorithms; D002621:Chemistry / Q000379:methods; D002627:Chemistry, Physical / Q000379:methods*; D015233:Models, Statistical; D008962:Models, Theoretical; D009991:Oscillometry; D010825:Physics / Q000379:methods; D011189:Potassium Chloride / Q000737:chemistry; D011789:Quantum Theory
D011189:Potassium Chloride