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

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


Titill: Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules
Höfundur: Ásgeirsson, Vilhjálmur
Bauer, Christoph A.
Grimme, Stefan
Útgáfa: 2017
Tungumál: Enska
Umfang: 4879-4895
Háskóli/Stofnun: Háskóli Íslands
University of Iceland
Svið: Verkfræði- og náttúruvísindasvið (HÍ)
School of Engineering and Natural Sciences (UI)
Deild: Raunvísindadeild (HÍ)
Faculty of Physical Sciences (UI)
Raunvísindastofnun (HÍ)
Science Institute (UI)
Birtist í: Chemical Science;8(7)
ISSN: 2041-6520
2041-6539 (eISSN)
DOI: 10.1039/c7sc00601b
Efnisorð: Skammtafræði
URI: https://hdl.handle.net/20.500.11815/366

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Tilvitnun:

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

Útdráttur:

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.

Leyfi:

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.

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