An experimental and theoretical study on structural parameters and energetics in ionization and dissociation of cobalt tricarbonyl nitrosyl

•Experimental and theoretical study on dissociative ionization of cobalt tricarbonyl nitrosyl.•Structural parameters on the two lowest spin states of Co(CO)3NO, [Co(CO)3NO]+ and their fragments.•Appearance energies for sequential ligand loss from [Co(CO)3NO]+ through dissociative ionization.•Threshold energies for sequential ligand loss from [Co(CO)3NO]+ through DFT calculations.•Theoretical and experimental bond dissociation energies for ligand loss from [Co(CO)3NO]+.

In a combined theoretical and experimental study we calculate the geometrical parameters, dipole moments and rotational constants for the two lowest spin states of Co(CO)3NO, i.e., the 1A1 and 3A states of the neutral as well as their positively charged counterparts; the 2A′ and 4A″ states of [Co(CO)3NO]+. The geometrical parameters are also calculated for the two lowest spin states of all possible (Co containing) positively charged fragments, resulting from ligand loss through dissociative ionization (DI) of Co(CO)3NO. From the lowest total energies resulting from the geometrical optimizations, we calculate the ionization energy for Co(CO)3NO and the threshold energies for the two lowest spin states of all possible fragments, as well as the respective bond dissociation energies (BDE) describing the sequential ligand loss. Further, through electron bombardment, we determine the ionization energy for Co(CO)3NO, the appearance energies (AEs) of all DI products observed and the BDE for individual ligand loss. Finally, the theoretical and experimental IEs, AEs and BDEs derived are compared and discussed in context to earlier electron ionization and threshold photoelectron-photoion coincidence spectroscopy (TPEPICO) studies.

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