Rotational molecular dynamics of laser-manipulated bromotrifluoromethane studied by x-ray absorption

We present a computational study of the rotational molecular dynamics of bromotrifluoromethane (CF3Br) molecules in gas phase. The rotation is manipulated with an off-resonant 800 nm laser. The molecules are treated as rigid rotors. Frequently, we use a computationally efficient linear rotor model for CF3Br, which we compare with selected results for full symmetric-rotor computations. The expectation value < cos(2) theta >(t) is discussed. Especially, the transition from impulsive to adiabatic alignment, the temperature dependence of the maximally achievable alignment, and its intensity dependence are investigated. In a next step, we examine resonant x-ray absorption as an accurate tool to study laser manipulation of molecular rotation. Specifically, we investigate the impact of the x-ray pulse duration on the signal (particularly its temporal resolution) and study the temperature dependence of the achievable absorption. Most importantly, we demonstrated that using picosecond x-ray pulses, one can accurately measure the expectation value < cos(2) theta >(t) for impulsively aligned CF3Br molecules. We point out that a control of the rotational dynamics opens up a novel way to imprint shapes onto long x-ray pulses on a picosecond time scale. For our computations, we determine the dynamic polarizability tensor of CF3Br using ab initio molecular linear-response theory in conjunction with wave function models of increasing sophistication: Coupled-cluster singles (CCS), second-order approximate coupled-cluster singles and doubles (CC2), and coupled-cluster singles and doubles (CCSD). (C) 2008 American Institute of Physics.