通过振动激发增强 H2O 在 Cu(111)上的离解化学吸附。
Enhancing dissociative chemisorption of H2O on Cu(111) via vibrational excitation.
机构信息
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
出版信息
Proc Natl Acad Sci U S A. 2012 Jun 26;109(26):10224-7. doi: 10.1073/pnas.1203895109. Epub 2012 Jun 8.
Abstract
The dissociative chemisorption of water is an important step in many heterogeneous catalytic processes. Here, the mode selectivity of this process was examined quantum mechanically on a realistic potential energy surface determined by fitting planewave density functional calculations spanning a large configuration space. The quantum dynamics of the surface reaction were characterized by a six-dimensional model including all important internal coordinates of H(2)O and its distance to the surface. It was found that excitations in all three vibrational modes are capable of enhancing reactivity more effectively than increasing translational energy, consistent with the "late" transition state in the reaction path.
摘要
水的离解化学吸附是许多多相催化过程中的重要步骤。在这里，通过拟合跨越大构型空间的平面波密度泛函计算，从量子力学的角度研究了该过程的模式选择性。表面反应的量子动力学由一个六维模型来描述，该模型包括 H(2)O 的所有重要的内部坐标及其与表面的距离。结果表明，三种振动模式的激发比增加平动能更有效地增强反应活性，这与反应途径中的“后期”过渡态一致。
相似文献
1
Enhancing dissociative chemisorption of H2O on Cu(111) via vibrational excitation.通过振动激发增强 H2O 在 Cu(111)上的离解化学吸附。
Proc Natl Acad Sci U S A. 2012 Jun 26;109(26):10224-7. doi: 10.1073/pnas.1203895109. Epub 2012 Jun 8.
2
Mode specificity for the dissociative chemisorption of H2O on Cu(111): a quantum dynamics study on an accurately fitted potential energy surface.H₂O在Cu(111)上解离化学吸附的模式特异性：基于精确拟合势能面的量子动力学研究
Phys Chem Chem Phys. 2016 Mar 28;18(12):8537-44. doi: 10.1039/c6cp00034g.
3
Effects of reactant internal excitation and orientation on dissociative chemisorption of H2O on Cu(111): quasi-seven-dimensional quantum dynamics on a refined potential energy surface.反应物内部激发和取向对 H2O 在 Cu(111)上离解化学吸附的影响：在精细势能表面上的准七维量子动力学。
J Chem Phys. 2013 Jan 28;138(4):044704. doi: 10.1063/1.4776770.
4
Mode specificity of water dissociating on Ni(100): An approximate full-dimensional quantum dynamics study.水在 Ni(100)表面上离解的模式特异性：近似全维量子动力学研究。
J Chem Phys. 2023 Jun 7;158(21). doi: 10.1063/5.0153538.
5
First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).基于第一性原理的量子动力学理论研究 H2O 在刚性 Cu(111)表面上的离解化学吸附。
Nat Commun. 2016 Jun 10;7:11953. doi: 10.1038/ncomms11953.
6
An approximate full-dimensional quantum dynamics study of the mode specificity in the dissociative chemisorption of DO on rigid Cu(111).关于DO在刚性Cu(111)表面解离化学吸附中模式特异性的近似全维量子动力学研究。
Phys Chem Chem Phys. 2017 May 17;19(19):11960-11967. doi: 10.1039/c7cp01770g.
7
Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity.多原子分子在过渡金属表面的离解化学吸附的量子动力学：模特异性和键选择性。
Chem Soc Rev. 2016 Jun 27;45(13):3621-40. doi: 10.1039/c5cs00360a.
8
Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).在甲醇在 Cu(111)上的离解化学吸附中，振动控制对选择性键断裂的影响。
Nat Commun. 2018 Oct 2;9(1):4039. doi: 10.1038/s41467-018-06478-6.
9
Vibrationally promoted dissociation of water on Ni(111).振动促进水在 Ni(111)上的离解。
Science. 2014 May 2;344(6183):504-7. doi: 10.1126/science.1251277.
10
Six-dimensional quantum dynamics of dissociative chemisorption of H2 on Co(0001) on an accurate global potential energy surface.H2 在 Co(0001)上离解化学吸附的六维量子动力学：基于精确全局势能面的研究。
Phys Chem Chem Phys. 2015 Sep 28;17(36):23346-55. doi: 10.1039/c5cp03324a.
引用本文的文献
1
Machine learning and data-driven methods in computational surface and interface science.计算表面与界面科学中的机器学习和数据驱动方法。
NPJ Comput Mater. 2025;11(1):196. doi: 10.1038/s41524-025-01691-6. Epub 2025 Jul 1.
2
Probing Water Dissociation and Oxygen Replacement on Partially Oxygen-Covered Cu(111) by Reflection Absorption Infrared Spectroscopy.通过反射吸收红外光谱法探究部分氧覆盖的Cu(111)表面的水离解和氧置换
J Phys Chem Lett. 2023 Sep 7;14(35):7848-7853. doi: 10.1021/acs.jpclett.3c02004. Epub 2023 Aug 25.
3
A seven-dimensional quantum dynamics study of the dissociative chemisorption of HO on Cu(111): effects of azimuthal angles and azimuthal angle-averaging.HO在Cu(111)表面解离化学吸附的七维量子动力学研究：方位角及方位角平均的影响
Chem Sci. 2016 Mar 1;7(3):1840-1845. doi: 10.1039/c5sc03689e. Epub 2015 Nov 25.
4
Rotational and steric effects in water dissociative chemisorption on Ni(111).水在Ni(111)表面解离化学吸附中的旋转和空间效应。
Chem Sci. 2017 Sep 1;8(9):6662-6669. doi: 10.1039/c7sc02659e. Epub 2017 Jul 26.
5
First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).基于第一性原理的量子动力学理论研究 H2O 在刚性 Cu(111)表面上的离解化学吸附。
Nat Commun. 2016 Jun 10;7:11953. doi: 10.1038/ncomms11953.
本文引用的文献
1
Dynamics of the reaction of methane with chlorine atom on an accurate potential energy surface.甲烷与氯原子反应的动力学：在精确势能表面上的研究。
Science. 2011 Oct 21;334(6054):343-6. doi: 10.1126/science.1208514.
2
The dissociative chemisorption of methane on Ni(100): reaction path description of mode-selective chemistry.甲烷在 Ni(100)上的离解化学吸附：模式选择性化学的反应路径描述。
J Chem Phys. 2011 Sep 21;135(11):114701. doi: 10.1063/1.3634073.
3
Calculation of multiple initial state selected reaction probabilities from Chebyshev flux-flux correlation functions: influence of reactant internal excitations on H + H2O → OH + H2.从 Chebyshev 通量-通量相关函数计算多个初始态选择反应概率：反应物内部激发对 H + H2O → OH + H2 的影响。
J Chem Phys. 2011 Aug 28;135(8):084112. doi: 10.1063/1.3626525.
4
High-dimensional ab initio potential energy surfaces for reaction dynamics calculations.高维从头计算势能面用于反应动力学计算。
Phys Chem Chem Phys. 2011 May 14;13(18):8094-111. doi: 10.1039/c0cp02722g. Epub 2011 Mar 11.
5
Quantum dynamics of dissociative chemisorption of CH(4) on Ni(111): Influence of the bending vibration.甲烷在镍（111）表面上离解化学吸附的量子动力学：弯曲振动的影响。
J Chem Phys. 2010 Oct 14;133(14):144308. doi: 10.1063/1.3491031.
6
Towards an understanding of the vibrational mode specificity for dissociative chemisorption of CH(4) on Ni(111): a 15 dimensional study.为了理解 CH(4)在 Ni(111)上的离解化学吸附的振动模式特异性：一项 15 维的研究。
Phys Chem Chem Phys. 2010 Jul 21;12(27):7654-61. doi: 10.1039/b924669j. Epub 2010 Jun 8.
7
CH stretching excitation in the early barrier F + CHD3 reaction inhibits CH bond cleavage.早期势垒F + CHD3反应中C-H伸缩激发抑制C-H键断裂。
Science. 2009 Jul 17;325(5938):303-6. doi: 10.1126/science.1175018.
8
Methane dissociation on Ni(111) and Pt(111): energetic and dynamical studies.甲烷在Ni(111)和Pt(111)上的解离：能量与动力学研究。
J Chem Phys. 2009 Feb 7;130(5):054701. doi: 10.1063/1.3065800.
9
Bond-selective control of a heterogeneously catalyzed reaction.多相催化反应的键选择性控制
Science. 2008 Feb 8;319(5864):790-3. doi: 10.1126/science.1152819.
10
On the mechanism of low-temperature water gas shift reaction on copper.关于铜上低温水煤气变换反应的机理
J Am Chem Soc. 2008 Jan 30;130(4):1402-14. doi: 10.1021/ja0768237. Epub 2008 Jan 9.
Zotero 插件