Please use this identifier to cite or link to this item:
Main Title: IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+-pi interaction
Author(s): Bouchet, Aude
Schütz, Markus
Chiavarino, Barbara
Crestoni, Maria Elisa
Fornarini, Simonetta
Dopfer, Otto
Type: Article
Language Code: en
Abstract: The structure and dynamics of the highly flexible side chain of (protonated) phenylethylamino neurotransmitters are essential for their function. The geometric, vibrational, and energetic properties of the protonated neutrotransmitter 2-phenylethylamine (H(+)PEA) are characterized in the N-H stretch range by infrared photodissociation (IRPD) spectroscopy of cold ions using rare gas tagging (Rg = Ne and Ar) and anharmonic calculations at the B3LYP-D3/(aug-)cc-pVTZ level including dispersion corrections. A single folded gauche conformer (G) protonated at the basic amino group and stabilized by an intramolecular NH+-pi interaction is observed. The dispersion-corrected density functional theory calculations reveal the important effects of dispersion on the cation-pi interaction and the large vibrational anharmonicity of the NH3+ group involved in the NH+-pi hydrogen bond. They allow for assigning overtone and combination bands and explain anomalous intensities observed in previous IR multiplephoton dissociation spectra. Comparison with neutral PEA reveals the large effects of protonation on the geometric and electronic structure.
Issue Date: 2015
Date Available: 25-Oct-2017
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: EC/FP7/600209/EU/International Post-Doc Initiative of the Technische Universität Berlin/IPODI
Journal Title: Physical chemistry, chemical physics
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 17
Issue: 39
Publisher DOI: 10.1039/c5cp00221d
Page Start: 25742
Page End: 25754
EISSN: 1463-9084
ISSN: 1463-9076
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:FG Lasermolekülspektroskopie und Umweltphysik » Publications

Files in This Item:
File Description SizeFormat 
c5cp00221d.pdf2.42 MBAdobe PDFThumbnail

Items in DepositOnce are protected by copyright, with all rights reserved, unless otherwise indicated.