General theory of population transfer by adiabatic rapid passage with intense, chirped laser pulses

We present a general theory of adiabatic rapid passage (ARP) with intense, linearly chirped laser pulses. For pulses with a Gaussian profile and a fixed bandwidth, we derive a rigorous formula for the maximum temporal chirp rate that can be sustained by the pulse. A modified Landau-Zener formula displays clearly the relationships among the pulse parameters. This formula is used to derive the optimal conditions for efficient, robust population transfer. As illustrations of the theory, we present results for two- and four-level systems, and selective vibronic excitation in the I2 molecule. We demonstrate that population transfer with chirped pulses is more robust and more selective than population transfer with transform-limited pulses.