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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited
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Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited

机译：活性热化学表：重新审视羟甲基（CH 2 OH）的分区功能

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摘要

The best currently available set of temperature dependent nonrigid rotor anharmonic oscillator (NRRAO) thermochemical and thermophysical properties of hydroxymethyl radical is presented. The underlying partition function relies on a critically evaluated complement of accurate experimental and theoretical data and is constructed using a two-pronged strategy that combines contributions from large amplitude motions obtained from direct counts, with contributions from the other internal modes of motion obtained from analytic NRRAO expressions. The contributions from the two strongly coupled large-amplitude motions of CH2OH, OH torsion and CH2 wag, are based on energy levels obtained by solving the appropriate two-dimensional projection of a fully dimensional potential energy surface that was recently obtained at the CCSD(T)/cc-pVTZ level of theory. The contributions of the remaining seven, more rigid, vibrational modes and of the external rotations are captured by NRRAO corrections to the standard rigid rotor harmonic oscillator (RRHO) treatment, which include corrections for vibrational anharmonicities, rotation-vibration interaction, Coriolis effects, and low temperature. The basic spectroscopic constants needed for the construction of the initial RRHO partition function rely on experimental ground-state rotational constants and the best available experimental fundamentals, additionally complemented by fundamentals obtained from the variational solution of the full-dimensional potential energy surface using a recently developed two-component multilayer Lanczos algorithm. The higher-order spectroscopic constants necessary for the NRRAO corrections are extracted from a second-order variational perturbation treatment (VPT2) of the same potential energy surface. The Lanczos solutions of the fully dimensional surface are validated against available experimental data, and the VPT2 results and the solutions of the reduced dimensionality surface are validated both against the
机译：提出了最佳的温度依赖性非侵入转子Anharmonic振荡器（NRRAO）热化学和热物理性质的羟甲基的热化学振荡器。潜在的分区功能依赖于准确评估的准确实验和理论数据的补充，并且使用两时庸的策略构造，该策略将来自直接计数获得的大振幅运动的贡献相结合，与来自分析NRRAO的其他内部运动模式的贡献表达。来自CH2OH，OH扭转和CH2摇摆的两个强大耦合的大幅度运动的贡献基于通过求解最近在CCSD（T的完全尺寸势能表面的适当二维投影）获得的能量水平（T. ）/ CC-PVTZ理论水平。 NRRAO校正对标准刚性转子谐振器（RRHO）处理的剩余七个，更刚性，振动模式和外部旋转的贡献，包括振动无谐波，旋转 - 振动相互作用，科里奥利效应和低温。建造初始RRHO分区功能所需的基本光谱常数依赖于实验地面旋转常数和最佳可用的实验基础，另外，通过最近开发的全维性潜在能量表面的变分溶液获得的基本原理互补双组分多层LanczoS算法。 NRRA校正所需的高阶光谱常数是从相同电位能量表面的二阶变分扰动处理（VPT2）中提取。全尺寸表面的LANCZOS溶液针对可用的实验数据验证，VPT2结果和减少的维度表面的溶液均被验证

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