Opin vísindi

Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules

Show simple item record

dc.contributor Háskóli Íslands
dc.contributor University of Iceland
dc.contributor.author Ásgeirsson, Vilhjálmur
dc.contributor.author Bauer, Christoph A.
dc.contributor.author Grimme, Stefan
dc.date.accessioned 2017-08-28T15:39:40Z
dc.date.available 2017-08-28T15:39:40Z
dc.date.issued 2017
dc.identifier.citation Asgeirsson, V., Bauer, C. A., & Grimme, S. (2017). Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules. Chemical Science, 8(7), 4879-4895. doi:10.1039/C7SC00601B
dc.identifier.issn 2041-6520
dc.identifier.issn 2041-6539 (eISSN)
dc.identifier.uri https://hdl.handle.net/20.500.11815/366
dc.description.abstract 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.
dc.description.sponsorship This work has been supported by DFG grant no. 1927/10-1, "First Principles Calculation of Electron Impact Mass Spectra of Molecules".
dc.format.extent 4879-4895
dc.language.iso en
dc.publisher Royal Society of Chemistry (RSC)
dc.relation.ispartofseries Chemical Science;8(7)
dc.rights info:eu-repo/semantics/openAccess
dc.subject Skammtafræði
dc.title Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules
dc.type info:eu-repo/semantics/article
dcterms.license This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.
dc.description.version Peer Reviewed
dc.identifier.journal Chemical Science
dc.identifier.doi 10.1039/c7sc00601b
dc.relation.url http://pubs.rsc.org/en/content/articlepdf/2017/SC/C7SC00601B
dc.contributor.department Raunvísindadeild (HÍ)
dc.contributor.department Faculty of Physical Sciences (UI)
dc.contributor.department Raunvísindastofnun (HÍ)
dc.contributor.department Science Institute (UI)
dc.contributor.school Verkfræði- og náttúruvísindasvið (HÍ)
dc.contributor.school School of Engineering and Natural Sciences (UI)

Files in this item

This item appears in the following Collection(s)

Show simple item record