First-Principles Study on Core-Level Spectroscopy of Arginine in Gas and Solid Phases
2012 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 116, no 42, 12641-12650 p.Article in journal (Refereed) Published
First-principles simulations have been performed for near-edge X-ray absorption fine-structure (NEXAFS) spectra of neutral arginine at different K-edges in the solid phase as well as X-ray photoelectron spectra (XPS) of neutral, deprotonated, and protonated arginines in the gas phase. Influences of the intra- and intermolecular hydrogen bonds (HBs) and different charge states have been carefully examined to obtain useful structure-property relationships. Our calculations show a noticeable difference in the NEXAFS/XPS spectra of the canonical and zwitterionic species that can be used for unambiguously identifying the dominant form in the gas phase. It is found that the deprotonation/protonation always results in red/blue shifts of several electronvolts for the core binding energies (BEs) at all edges. The normal hydrogen bond Y-H center dot center dot center dot X (X, Y = N, O) can cause a blue/red shift of ca. 1 eV to the core BEs of the proton acceptor X/donor Y, while the weak C-H center dot center dot center dot Y hydrogen bond may also lead to a weak red shift (less than 1 eV) of the C1s BEs. Moreover, the influence of intermolecular interactions in the solid state is reflected as a broadening in the sigma* region of the NEXAFS spectra at each edge, while in the pi* region, these interactions lead to a strengthening or weakening of individual transitions from different carbons, although no evident visual change is found in the resolved total spectra. Our results provide a better understanding of the influences of the intra- and intermolecular forces on the electronic structure of arginine.
Place, publisher, year, edition, pages
2012. Vol. 116, no 42, 12641-12650 p.
X-Ray-Absorption, Photoelectron Binding-Energies, Amino-Acids, Fine-Structure, Liquid Water, Electron Spectroscopy, Chemical Analysis, Hydrogen-Bonds, Glycine, Spectra
IdentifiersURN: urn:nbn:se:kth:diva-106131DOI: 10.1021/jp302309uISI: 000310120900001ScopusID: 2-s2.0-84867819204OAI: oai:DiVA.org:kth-106131DiVA: diva2:573642
QC 201212032012-12-032012-11-292014-05-22Bibliographically approved