Correlating the orbital overlap area and vibrational frequency shift of an isocyanide moiety adsorbed on Pt and Pd covered Au(111) surfaces

Zhang, Xia-Guang1; Zhong, Jin-Hui2

2022-09-01

10.1039/d2cp03444a

PHYSICAL CHEMISTRY CHEMICAL PHYSICS   Impact Factor & Quartile

1463-9076

1463-9084

Orbital interactions between adsorbed molecules and the underlying metal surfaces play critical roles in a wide range of surface and interfacial processes. Establishing a correlation between an experimental observable (e.g., vibrational frequency shift of the adsorbed molecule) and the orbital interactions is of vital importance. Herein, theoretical calculations are used to investigate the vibrational frequency shift of phenyl isocyanide molecules as a probe molecule adsorbed on mono- and bi-layer Pt and Pd covered Au(111) surfaces and Pd2Au4 and Pt2Au4 clusters. By analyzing the density of states (DOS) of the adsorption system, we show that the orbital overlap area of d electronic DOS with a molecular sigma or pi* orbital, particularly their ratio (Rd-sigma/d-pi*), can be a meaningful descriptor to explain the frequency shift of the C N moiety. This hypothesis has been verified by simulations for phenyl isocyanide with electron donating NH2- and withdrawing CF3- substituent groups, formonitrile and carbon monoxide. Quasi-linear dependence of the frequency shift on Rd-sigma/d-pi* is observed for both the red and blue shift regions. Our findings build up on previous notions of electronic interactions, which will provide a more quantitative and solid footing to understand and analyze the frequency shift of adsorbed molecules on metal surfaces and the related electronic interactions and catalytic properties.

SCI

English

Corresponding

National Natural Science Foundation of China (NSFC)["22002036","22272072"] ; Natural Science Foundation of Henan Province[202300410234]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:000859995100001

ROYAL SOC CHEMISTRY

CHEMISTRY

Web of Science

1.Henan Normal Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Henan Prov Green Mfg Fine, Key Lab Green Chem Media & React,Minist Educ, Xinxiang 453007, Henan, Peoples R China
2.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China

Zhang, Xia-Guang,Zhong, Jin-Hui. Correlating the orbital overlap area and vibrational frequency shift of an isocyanide moiety adsorbed on Pt and Pd covered Au(111) surfaces[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2022.

Zhang, Xia-Guang,&Zhong, Jin-Hui.(2022).Correlating the orbital overlap area and vibrational frequency shift of an isocyanide moiety adsorbed on Pt and Pd covered Au(111) surfaces.PHYSICAL CHEMISTRY CHEMICAL PHYSICS.

Zhang, Xia-Guang,et al."Correlating the orbital overlap area and vibrational frequency shift of an isocyanide moiety adsorbed on Pt and Pd covered Au(111) surfaces".PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2022).