Vibrational populations as a function of time for the laser loop encircling the maximum transfer peak (7,8) corresponding to a pulse duration <em>T</em><sub>max</sub> = 50 fs

<p><strong>Figure 5.</strong> Vibrational populations as a function of time for the laser loop encircling the maximum transfer peak (7,8) corresponding to a pulse duration <em>T</em><sub>max</sub> = 50 fs. (a) The initial bound state is <em>v</em> = 7. Solid black line for P_{7,7}^{{\rm WP}}, dashed red line for P_{8,7}^{{\rm WP}} and dotted blue line for P_{6,7}^{{\rm WP}}. (b) The initial bound state is <em>v</em> = 8. Solid black line for P_{7,8}^{{\rm WP}}, dashed red line for P_{8,8}^{{\rm WP}} and dashed-dotted green line for P_{9,8}^{{\rm WP}}.</p> <p><strong>Abstract</strong></p> <p>Laser control schemes for selective population inversion between molecular vibrational states have recently been proposed in the context of molecular cooling strategies using the so-called exceptional points (corresponding to a couple of coalescing resonances). All these proposals rest on the predictions of a purely adiabatic Floquet theory. In this work we compare the Floquet model with an exact wavepacket propagation taking into account the accompanying non-adiabatic effects. We search for signatures of a given exceptional point in the wavepacket dynamics and we discuss the role of the non-adiabatic interaction between the resonances blurring the ideal Floquet scheme. Moreover, we derive an optimal laser field to achieve, within acceptable compromise and rationalizing the unavoidable non-adiabatic contamination, the expected population inversions. The molecular system taken as an illustrative example is H_{2}^{+}.</p>