Nonadiabatic Photodissociation of the Hydroxymethyl Radical from the 22A State. Surface Hopping Simulations Based on a Full Nine-Dimensional Representation of the 1,2,32A Potenti

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• 作者：Christopher L. Malbon ; David R. Yarkony
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：July 16, 2015
• 年：2015
• 卷：119
• 期：28
• 页码：7498-7509
• 全文大小：721K
• ISSN：1520-5215

文摘

The nonadiabatic photodissociation CH₂OH(1²A) + hv 鈫?CH₂OH(2,3²A) 鈫?CH₂O + H or HCOH(cis or trans) + H is addressed using trajectory surface hopping dynamics on a quasi-diabatic representation, H^d, of the 1,2,3²A coupled, adiabatic potential energy surfaces. We focus on dynamics originating on the 2²A potential energy surface. The H^d is based exclusively on electronic structure data obtained from a multireference configuration interaction single and double excitation expansion, composed of over 67 million configuration state functions, and treats all nine internal degrees of freedom in an even-handed manner. Each simulation is based on bundles of 10000 trajectories randomly selected from harmonic Wigner distributions and propagated for up to 1 ps. The bimodal distribution in the kinetic energy release spectrum is explained in terms of direct versus quasi-statistical dissociation.