## Abstract

This paper presents pulsed-field ionization, zero electron kinetic energy (ZEKE) photoelectron and threshold photoionization spectra of M-X(CH _{3})_{3} (M = Ga, In; X = P, As). The ZEKE spectra exhibit well-resolved vibrational structures. A comparison with B3LYP calculations shows that the spectrum of In-P(CH_{3})_{3} arises from the ^{1}A_{1} ← ^{2}E transition and the spectra of Ga-P(CH_{3})_{3} and Ga-As(CH_{3})_{3} arise from transitions of a Jahn-Teller distorted doublet state to the ^{1}A_{1} state. The intensities of the ^{}1A _{1}-^{2}E transition in the indium species are described with the Franck-Condon approximation, while the transitions in the gallium complexes are more complicated due to the dynamic Jahn-Teller effect. The adiabatic ionization potentials of Ga-P(CH_{3})_{3}, In-P(CH _{3})_{3}, and Ga-As(CH_{3})_{3} are 39 635, 38 930, and 40 322 cm^{-1}, respectively, and the ionization threshold of In-As(CH_{3})_{3} is ∼39 550 cm^{-1}. The metal-ligand stretching frequencies are 143, 116, and 125 cm^{-1} for Ga^{+}-P, In^{+}-P, and Ga^{+}-As. respectively, and 96 cm^{-1} for In-P. The intermolecular bending frequencies are 71, 65, and 42 cm^{-1} for Ga^{+}-P-C, In^{+}-P-C, and Ga ^{+}-As-C, respectively, and 47 cm^{-1} for In-P-C. In addition, ligand-based vibrational frequencies are determined for the CH_{3} wag, PC_{3} and AsC_{3} umbrella, and P-C stretching vibrations.

Original language | English |
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Pages (from-to) | 1067-1076 |

Number of pages | 10 |

Journal | Canadian Journal of Chemistry |

Volume | 82 |

Issue number | 6 |

DOIs | |

State | Published - Jun 2004 |

## Keywords

- DFT
- Gallium-arsine
- Gallium-phosphine
- Indium-arsine
- Indium-phosphine
- Photoionization
- ZEKE photoelectron

## ASJC Scopus subject areas

- Catalysis
- General Chemistry
- Organic Chemistry

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