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Title: Guanidine and guanidinium cation in the excited state—theoretical investigation

Diverse ab initio and density-functional-theory methods were used to investigate geometries, energies, and electronic absorption spectra of guanidine and its protonated form, as well as their photo-deactivation processes. It was shown that the guanidine is a weakly absorbing species with the excitation spectrum consisting mostly of transitions to the Rydberg excited states and one valence n-π{sub 4} state. The lowest energy band has a maximum at ca. 6.9 eV (∼180 nm). The protonation of guanidine affects its excitation spectrum substantially. A major shift of the Rydberg states to higher energies is clearly visible and strongly absorbing transitions from the ground state to the π{sub 3}-π{sub 4} and π{sub 2}-π{sub 4} states appears at 7.8 eV (∼160 nm). Three low-lying conical intersections (two for guanidine and one for protonated guanidine) between the ground state and the first excited singlet state were located. They are accessible from the Franck–Condon region through amino N–H stretching and out-of-plane deformations in guanidine and protonated guanidine, respectively. The relaxation of the π{sub 3}-3s Rydberg state via amino N–H bond stretching was hindered by a barrier. The nondissociated conical intersection in protonated guanidine mediates the radiationless deactivation of the compound after excitation into the π{sub 3}-π{sub 4}more » state. This fact is detrimental for the photostability of guanidine, since its conjugate acid is stable in aqueous solution over a wide pH range and in protein environment, where guanidinium moiety in arginine is expected to be in a protonated form.« less
Authors:
;  [1] ; ;  [2]
  1. Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, P.O. Box 180, HR-10002 Zagreb (Croatia)
  2. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr (Germany)
Publication Date:
OSTI Identifier:
22419795
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 7; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; AQUEOUS SOLUTIONS; CATIONS; DEACTIVATION; DENSITY FUNCTIONAL METHOD; EXCITATION; GROUND STATES; PROTEINS; RYDBERG STATES