Issue 39, 2015

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+–π interaction

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+–π interaction is observed. The dispersion-corrected density functional theory calculations reveal the important effects of dispersion on the cation–π interaction and the large vibrational anharmonicity of the NH3+ group involved in the NH+–π hydrogen bond. They allow for assigning overtone and combination bands and explain anomalous intensities observed in previous IR multiple-photon dissociation spectra. Comparison with neutral PEA reveals the large effects of protonation on the geometric and electronic structure.

Graphical abstract: IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+–π interaction

Supplementary files

Article information

Article type
Paper
Submitted
14 Jan 2015
Accepted
25 Feb 2015
First published
26 Feb 2015

Phys. Chem. Chem. Phys., 2015,17, 25742-25754

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+–π interaction

A. Bouchet, M. Schütz, B. Chiavarino, M. Elisa Crestoni, S. Fornarini and O. Dopfer, Phys. Chem. Chem. Phys., 2015, 17, 25742 DOI: 10.1039/C5CP00221D

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