SYMMETRIC ROTOR LINE STRENGTH FACTORS IN ZEKE-PFI SPECTRA
Loading...
Date
1998
Authors
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
In the two color ZEKE-PFI $study^{a}$ of the $CdCH_{3}$ radical well-resolved K rotational structure has been observed in some vibronic states. We have extended the previous theoretical formulation of the selection $rules^{b}$ to cover the observed transitions. An important result is that the selection rules are determined by the vibronic structure of the intermediate state of the neutral from which the ionizing ZEKE transition occurs. For example, the H\""{o}nl-London-type line strength factor S for the ionizing $e - e$ vibronic transition can be written as $S(N^{+}K^{+}p^{+};NKp)=\delta_{p^{+},-p}(2N^{+}+1)(2N+1) \sum\limits_{l_{A},\lambda_{A}=1,-2,A,-5,\ldots}a^{2}_{l_{A}\lambda_{A}} A_{t_{A}NN^{+}} \left(\begin{array}{ccc}N^{+}&l_{A}&N\\-K^{+}&-\lambda_{A}&-K\end{array}\right)^{2},$ where p denotes the state's parity and the $A_{l_{A}NN^{+}}$ are determined by the wavepacket composition of the Rydberg state that is subsequently field ionized. The $a_{l_{A}\lambda_{A}}$ are coefficients in an expansion of the neutral state's vibronic wavefunction $|\phi\rangle$ in terms of a core wavefunction $|\phi_{cor}\rangle$, its vibrational wavefunctions $|\phi_{vlb}\rangle$, and its single electron atomic wavefunctions $|l_{A}, \lambda_{A}\rangle$: $|\phi\rangle=|\phi_{cor}\rangle \sum\limits_{l_{A},\lambda_{A}} a_{l_{A} \lambda_{A} |\phi_{vib}}\rangle |l_{A}, \lambda_{A}\rangle$
Description
$^{a}$ S.I. Panov, David E. Powers and T.A. Miller J. Chem. Phys. 108 1335 (1998). $^{b}$ Klaus M\""{u}ller-Dethlefs J. Chem. Phys. 95 4821 (1991).
Author Institution: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA; Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, Columbus, OH
Author Institution: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA; Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, Columbus, OH