Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules† †Electronic supplementary information (ESI) available: GFN-xTB calculated potential energy surfaces for example coordinates. Additional calculated mass spectra. Computational timing statistics. See DOI: 10.1039/c7sc00601b Click here for additional data file

• Published in: Chemical science (Cambridge) Vol. 8; no. 7; pp. 4879 - 4895
• Main Authors: Ásgeirsson, Vilhjálmur, Bauer, Christoph A., Grimme, Stefan
• Format: Journal Article
• Language: English
• Published: Royal Society of Chemistry 05.05.2017
• Subjects: Chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c7sc00601b

The implementation of a novel tight-binding Hamiltonian within the QCEIMS program allows the first-principles based computation of EI mass spectra within a few hours for systems containing elements up to Z = 86. We introduce a fully stand-alone version of the Quantum Chemistry Electron Ionization Mass Spectra (QCEIMS) program [S. Grimme, Angew. Chem. Int. Ed. , 2013, 52 , 6306] allowing efficient simulations for molecules composed of elements with atomic numbers up to Z = 86. The recently developed extended tight-binding semi-empirical method GFN-xTB has been combined with QCEIMS, thereby eliminating dependencies on third-party electronic structure software. Furthermore, for reasonable calculations of ionization potentials, as required by the method, a second tight-binding variant, IPEA-xTB, is introduced here. This novel combination of methods allows the automatic, fast and reasonably accurate computation of electron ionization mass spectra for structurally different molecules across the periodic table. In order to validate and inspect the transferability of the method, we perform large-scale simulations for some representative organic, organometallic, and main-group inorganic systems. Theoretical spectra for 23 molecules are compared directly to experimental data taken from standard databases. For the first time, realistic quantum chemistry based EI-MS for organometallic systems like ferrocene or copper( ii )acetylacetonate are presented. Compared to previously used semiempirical methods, GFN-xTB is faster, more robust, and yields overall higher quality spectra. The partially analysed theoretical reaction and fragmentation mechanisms are chemically reasonable and reveal in unprecedented detail the extreme complexity of high energy gas phase ion chemistry including complicated rearrangement reactions prior to dissociation.