Effect of Basicity and Structure on the Hydration of Protonated Molecules, Proton-Bound Dimer and Cluster Formation: An Ion Mobility-Time of Flight Mass Spectrometry and Theoretical Study

  • Younes ValadbeigiEmail author
  • Vahideh Ilbeigi
  • Bartosz Michalczuk
  • Martin Sabo
  • Stefan MatejcikEmail author
Research Article


Protonation, hydration, and cluster formation of ammonia, formaldehyde, formic acid, acetone, butanone, 2-ocatanone, 2-nonanone, acetophenone, ethanol, pyridine, and its derivatives were studied by IMS-TOFMS technique equipped with a corona discharge ion source. It was found that tendency of the protonated molecules, MH+, to participate in hydration or cluster formation depends on the basicity of M. The molecules with higher basicity were hydrated less than those with lower basicity. The mass spectra of the low basic molecules such as formaldehyde exhibited larger clusters of MnH+(H2O)n, while for compounds with high basicity such as pyridine, only MH+ and MH+M peaks were observed. The results of DFT calculations show that enthalpies of hydrations and cluster formation decrease as basicities of the molecules increases. Using comparison of mass spectra of formic acid, formaldehyde, and ethanol, effect of structure on the cluster formation was also investigated. Formation of symmetric (MH+M) and asymmetric proton-bound dimers (MH+N) was studied by ion mobility and mass spectrometry techniques. Both theoretical and experimental results show that asymmetric dimers are formed more easily between molecules (M and N) with comparable basicity. As the basicity difference between M and N increases, the enthalpy of MH+N formation decreases.


Proton affinity Clustering Hydration Proton-bound dimer Mass spectrometry 



This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 692335 and Marie skłodowska-Curie grant agreement no. 674911. This work was supported by the Slovak Research and Development Agency (contract nos. APVV-0259-12 and APVV-15-0580) and the Slovak Grant Agency for Science (contract no. VEGA 1/0787/18). YV thanks HPC Computing Facility of IKIU, Iran, for computational resources.

Supplementary material

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Copyright information

© American Society for Mass Spectrometry 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of ScienceImam Khomeini International UniversityQazvinIran
  2. 2.TOF Tech. Pars CompanyIsfahanIran
  3. 3.Department of Experimental PhysicsComenius UniversityBratislavaSlovak Republic

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