Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction.
Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction.
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DOI：
10.1021/acs.jpclett.6b01022
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发表时间：
2016-07-07
期刊：
影响因子：
--
通讯作者：
Utz AL
中科院分区：
文献类型：
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作者：
Nattino F;Migliorini D;Kroes GJ;Dombrowski E;High EA;Killelea DR;Utz AL
虽然对多相催化很重要，但精确模拟多原子分子与金属表面反应的能力还没有跟上气相动力学的发展。将密度泛函理论的特定反应参数（SRP）方法与从头算分子动力学（AIMD）相结合，扩展了我们对金属反应的定量准确性建模能力，从最轻的反应物H2到基本上所有的分子。这通过对CHD 3 + Ni（111）的AIMD计算得到证明，其中SRP泛函与超声束实验相拟合，并通过显示具有所得泛函的AIMD以化学精度（4.2 kJ/mol至1 kcal/mol）再现初始状态选择的粘附测量来验证。只需要半局域交换，使我们的计划在计算上易于处理的过渡金属上的解离。
Although important to heterogeneous catalysis, the ability to accurately model reactions of polyatomic molecules with metal surfaces has not kept pace with developments in gas phase dynamics. Partnering the specific reaction parameter (SRP) approach to density functional theory with ab initio molecular dynamics (AIMD) extends our ability to model reactions with metals with quantitative accuracy from only the lightest reactant, H2, to essentially all molecules. This is demonstrated with AIMD calculations on CHD3 + Ni(111) in which the SRP functional is fitted to supersonic beam experiments, and validated by showing that AIMD with the resulting functional reproduces initial-state selected sticking measurements with chemical accuracy (4.2 kJ/mol ≈ 1 kcal/mol). The need for only semilocal exchange makes our scheme computationally tractable for dissociation on transition metals.