Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

Shukla, Anil; Bogdanov, Bogdan

doi:10.1063/1.4907366

Title: Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

Journal Article · Tue Feb 10 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4907366· OSTI ID:1274887

Shukla, Anil ^[1]; Bogdanov, Bogdan ^[2]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
San Jose Technology Center, San Jose, CA (United States)

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry. Singly as well as multiply charged clusters were formed with the general formulae, (HCOOLi)_nLi⁺, (HCOOLi)_nLi_m^m+, (HCOOLi)_nHCOO^- and (HCOOLi)_n(HCOO)_m^m-. Several magic number cluster ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)₃Li⁺ being the most abundant and stable cluster ions. Fragmentations of singly charged clusters proceed first by the loss of a dimer unit ((HCOOLi)₂) followed by sequential loss of monomer units (HCOOLi). In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)₃Li⁺ at higher collision energies which later fragments to dimer and monomer ions in lower abundance. Quantum mechanical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Lastly, thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1274887

Report Number(s):: PNNL-SA-106023; KP1704020

Journal Information:: Journal of Chemical Physics, Vol. 142, Issue 6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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Title: Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

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