High-resolution infrared spectroscopy of the charge-transfer complex [Ar-N2]+: a combined experimental/theoretical study.
A combined experimental and theoretical study of the charge-transfer complex [Ar-N(2)](+) is presented. Nearly 50 transitions split by spin-rotation interaction have been observed by means of infrared diode laser absorption spectroscopy in a supersonic planar plasma expansion. The band origin is at 2272.2563(18) cm(-1) and rotational constants in the ground and vibrationally (NN-stretch) excited state amount to 0.128701(8) cm(-1) and 0.128203(8) cm(-1), respectively. The interpretation of the data in terms of a charge switch upon complexation is supported by new ab initio calculations. The best estimate for a linear equilibrium structure yields R(e)(NN)=1.102 A and R(e)(Ar-N)=2.190 A. Predictions for molecular parameters not directly available from the experimental results are presented as well. Furthermore, the electronic structure and Ar-N bonding mechanism of [Ar-N(2)](+) have been analyzed in detail. The Ar-N bond is a textbook example of a classical 2-center-3-electron bond.
Verbraak
H
H
Laser Centre Amsterdam, Department of Physical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands.
van Stralen
J N P
JN
Bouwman
J
J
de Klerk
J S
JS
Verdes
D
D
Linnartz
H
H
Bickelhaupt
F M
FM