AI 中文总结
研究利用新形式的振转哈密顿量及精确势能面，计算H₂ + D → HD + H反应在75 - 800 K的速率系数，强调对分子旋转和核自旋对称性的精确处理，实现反应速率系数的高效直接量子力学计算。
AI 中文摘要
研究表明，对热反应速率系数进行高效、直接且完全量子力学的计算，需要一种新的、部分重排形式的振转哈密顿量的数值构建精确动能部分，该部分用内坐标表示。利用此哈密顿量和由Mielke、Garrett和Peterson开发的表征H₂ + H交换反应的精确全维势能面，计算了H₂ + D → HD + H反应在75 - 800 K温度范围内的反应速率系数。本文特别强调了对整体分子旋转的精确处理和核自旋对称性。
英文摘要
It is shown that an efficient, direct, and fully quantum mechanical calculation of thermal reaction rate coefficients requires a new, partially rearranged form of the numerically-constructed exact kinetic energy part of the rovibrational Hamiltonian expressed in internal coordinates. Using this Hamiltonian and an accurate, full-dimensional potential energy surface characterizing the H$_2$ + H exchange reaction, developed by Mielke, Garrett, and Peterson (J. Chem. Phys. 2002, 116, 4142), reaction rate coefficients in the temperature range of $75-800$ K have been computed for the H$_2$ + D $\rightarrow$ HD + H reaction. The paper puts particular emphasis on the exact treatment of overall molecular rotation and on nuclear spin symmetry.
