Beam broadening of polar molecules and clusters in deflection experiments

Details Beam broadening of polar molecules and clusters in deflection experiments Beam broadening of polar molecules and clusters in deflection experiments

2011-12-13

arxiv.org/abs/1112.3049v1

J. Chem. Phys. 136, 014301 (2012)

Physics

Atomic and Molecular Clusters

To be published in the Journal of Chemical Physics

Scientific paper

10.1063/1.3673890

A beam of rotating dipolar particles (molecules or clusters) will broaden when passed through an electric or magnetic field gradient region. This broadening, which is a common experimental observable, can be expressed in terms of the variance of the distribution of the resulting polarization orientation (the direction cosine). Here the broadening for symmetric-top and linear rotors is discussed. These two types of rotors have qualitatively different low-field orientation distribution functions, but behave similarly in a strong field. While analytical expressions for the polarization variance can be derived from first-order perturbation theory, for experimental guidance it is important to identify the applicability and limitations of these expressions, and the general dependence of the broadening on the experimental parameters. For this purpose, the analytical results are compared with the full diagonalization of the rotational Stark-effect matrices. Conveniently for experimental estimations, it is found that for symmetric tops the dependence of the broadening parameter on the rotational constant, the axial ratio, and the field strength remains similar to the analytical expression even outside of the perturbative regime. Also, it is observed that the shape envelope, the centroid, and the width of the orientation distribution function for a symmetric top are quite insensitive to the value of its rotational constant (except at low rotational temperatures).

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