Manipulating intracluster ion-molecule reactions via the control of vibrational excitation states of the parent cluster ion holds significant promise. Herein, we studied the effect of vibrational excitation on intracluster ion-molecule reactions within the ethylene dimer ion ${\left({\mathrm{C}}_2{\mathrm{H}}_4\right)}_2{}^{+}$ focusing on the formation of ${\mathrm{C}}_4{\mathrm{H}}_8{}^{+}, {\mathrm{C}}_3{\mathrm{H}}_5{}^{+}$, and ${\mathrm{C}}_4{\mathrm{H}}_7{}^{+}$ ions, utilizing femtosecond laser pulses and ab initio calculations. Via coincident photoelectron and ion detection, we reconstructed the initial vibrational excitation state population (IVP) of the parent ion and found a correlation between the IVP and product formation. Our study shows that the branching ratios for ${\mathrm{C}}_4{\mathrm{H}}_8{}^{+}, {\mathrm{C}}_4{\mathrm{H}}_7^{+}$, and ${\mathrm{C}}_3{\mathrm{H}}_5^{+}$ ions are dominated by low, medium, and high vibrational states, respectively, and there is a clear competition among them. Further analysis confirmed that laser intensity affects the IVP, which determines the yield of each decay channel. Our study establishes a direct link between IVP and product distribution in intracluster ion-molecule reactions and demonstrates the potential to steer reaction outcomes by varying laser field intensity, which opens avenues to the tailored control of reactions in various intracluster systems.

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• Atomic & molecular clusters
• Laser-cluster interaction
• Molecular dissociation
• Potential energy surfaces
• Ultracold collisions
• Vibrational states
• Clusters
• Molecular dynamics
• Photoionization