Intense pulsed-laser fields have provided means to both induce spatial alignment of molecules and enhance strength of chemical bonds. The duration of the laser field typically ranges from hundreds of picoseconds to a few femtoseconds. Accordingly, the induced "laser-dressed" properties can be adiabatic, existing only during the pulse, or nonadiabatic, persisting into the subsequent field-free domain. We exemplify these aspects by treating the helium dimer, in its ground [Formula: see text] and first excited [Formula: see text] electronic states. The ground-state dimer when field-free is barely bound, so very responsive to electric fields. We examine two laser realms, designated (I) "intrusive" and (II) "impelling." I employs intense nonresonant laser fields, not strong enough to dislodge electrons, yet interact with the dimer polarizability to induce binding and pendular states in which the dimer axis librates about the electric field direction. II employs superintense high-frequency fields that impel the electrons to undergo quiver oscillations, which interact with the intrinsic Coulomb forces to form an effective binding potential. The dimer bond then becomes much stronger. For I, we map laser-induced pendular alignment within the X state, which is absent for the field-free dimer. For II, we evaluate vibronic transitions from the X to A states, governed by the amplitude of the quiver oscillations.
Keywords: Kramers–Henneberger approximation; chemical bonding; laser-induced properties; pendular alignment; quiver oscillations.
Conflict of interest statement
The authors declare no conflict of interest.
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