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 σ or π* orbital, particularly their ratio (R_{d–σ/d–π*}), can be a meaningful descriptor to explain the frequency shift of the CN 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 R_{d–σ/d–π*} 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.