Mode selectivity with polarization shaping in the mid-IR.

We report that polarization-shaped mid-infrared (IR) pulses can be used to enhance the vibrational population of one mode over another in a coupled molecular system. A genetic algorithm and a new mid-IR polarization shaper were used to alter the relative vibrational excitation of the two carbonyl stretching modes in Mn(CO)(5)Br. One mode could be selectively enhanced over the other by 2-3 times. Control over the polarization leads to better optimization than phase-only control. Several possible mechanisms that indicate how polarization shaping leads to selective vibrational excitation are discussed using a formalism that separates polarization shaping effects on the signal strength from amplitude or phase shaping. The techniques introduced herein will have broad applications in quantum gating schemes, controlling ground state chemistry and enhancing the sensitivity of multidimensional IR and visible spectroscopies.