TY - JOUR
T1 - Zero electron kinetic energy photoelectron and threshold photoionization spectroscopy of M-X(CH3)3 (M= Ga, In; X = P, As)
AU - Li, Shenggang
AU - Rothschopf, Gretchen K.
AU - Sohnlein, Bradford R.
AU - Fuller, Jason F.
AU - Yang, Dong Sheng
PY - 2004/6
Y1 - 2004/6
N2 - 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(CH3)3 arises from the 1A1 ← 2E transition and the spectra of Ga-P(CH3)3 and Ga-As(CH3)3 arise from transitions of a Jahn-Teller distorted doublet state to the 1A1 state. The intensities of the 1A 1-2E 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(CH3)3, In-P(CH 3)3, and Ga-As(CH3)3 are 39 635, 38 930, and 40 322 cm-1, respectively, and the ionization threshold of In-As(CH3)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 CH3 wag, PC3 and AsC3 umbrella, and P-C stretching vibrations.
AB - 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(CH3)3 arises from the 1A1 ← 2E transition and the spectra of Ga-P(CH3)3 and Ga-As(CH3)3 arise from transitions of a Jahn-Teller distorted doublet state to the 1A1 state. The intensities of the 1A 1-2E 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(CH3)3, In-P(CH 3)3, and Ga-As(CH3)3 are 39 635, 38 930, and 40 322 cm-1, respectively, and the ionization threshold of In-As(CH3)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 CH3 wag, PC3 and AsC3 umbrella, and P-C stretching vibrations.
KW - DFT
KW - Gallium-arsine
KW - Gallium-phosphine
KW - Indium-arsine
KW - Indium-phosphine
KW - Photoionization
KW - ZEKE photoelectron
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U2 - 10.1139/v04-053
DO - 10.1139/v04-053
M3 - Article
AN - SCOPUS:9944254589
SN - 0008-4042
VL - 82
SP - 1067
EP - 1076
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
IS - 6
ER -