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• W1609875058 endingPage "8789" @default.
• W1609875058 startingPage "8785" @default.
• W1609875058 abstract "The reaction Li(2 2PJ)+H2(v=1)→LiH(X 1Σ+)+H is studied to understand the effect of vibrational excitation on the reaction pathways. The hydrogen molecules in the v=1, j=0–3 levels are populated by using stimulated Raman pumping (SRP). A pump–probe technique is employed simultaneously to initiate the reaction and monitor the products. The pump–SRP and SRP–probe delay time are short enough to allow for the products to be in a nascent state. The population fraction in the v=1 level can be estimated to be 7.5% by using coherent anti-Stokes Raman spectroscopy. As characterized by Boltzmann rotational temperature of 730 K, the rotational state distributions of LiH(v=0) obtained with H2(v=1) appear to be unimodal, similar to those obtained with H2(v=0), but the product yield is enhanced by a factor of 7–8 times. According to the potential energy surfaces calculations, the insertion mechanism in (near) C2v collision configuration is favored. The Li(2 2PJ)–H2 collision is initially along the 2A′ surface in the entrance channel and then transits to the ground 1A′ surface, from which the products are formed. When H2 stretches to its outer turning point (∼0.9 Å), the 2A′ surface may diabatically couple to the 1A′ surface in the attractive region. An energy barrier of 4300 cm−1 will otherwise obscure the reaction if the H2 bond distance is fixed at 0.75 Å. The energy deposited in the v=1 level simply enlarges the H2 bond distance to help facilitate the reaction and increase the subsequent product yield. The lack of detection of the product LiH(v⩾1) implies that the exoergic energy by 2530 cm−1 should not be distributed statistically among different freedom of motions. The vibrational excitation does not seem to open up an additional pathway for the reaction." @default.
• W1609875058 created "2016-06-24" @default.
• W1609875058 creator A5052525233 @default.
• W1609875058 creator A5074881833 @default.
• W1609875058 date "2003-10-17" @default.
• W1609875058 modified "2023-10-03" @default.
• W1609875058 title "Influence of vibrational excitation on the reaction Li(2 2PJ)+H2(v=1)→LiH(X 1Σ+)+H" @default.
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• W1609875058 doi "https://doi.org/10.1063/1.1620997" @default.
• W1609875058 hasPublicationYear "2003" @default.
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