Probability Density Analysis Reveals Substantial Differences Between the Dinitrogen and Acetylene Triple Bonds

Journal of Computational Chemistry, vol. 46, pp. e70037

Abstract

ABSTRACT In earlier publications, it was shown that the electron positions maximizing the probability density resemble the Lewis structures for most small molecules. While this holds for the triple bond in acetylene, this is not the case for the triple bond in dinitrogen. Because of recent advances in studying the topology of wave functions, this peculiar case is revisited. In this work, the dinitrogen wave function is analyzed and compared to that of acetylene. Significant differences of the electron positions maximizing are uncovered and explained by the presence of hydrogen atoms in acetylene and by electron arrangements resulting from calculations of the nitrogen and carbon atoms. Moreover, insights into the electron delocalization of both molecules are gained by investigating electron exchange paths. Considering the different chemical behaviors of dinitrogen and acetylene, these differences should be expected.

Authors 4

1. Michel V. Heinz Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry RWTH Aachen University Aachen Germany

   Institute of Physical Chemistry, RWTH Aachen University, Aachen, Germany

2. Emma Gorgas Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry RWTH Aachen University Aachen Germany

   Institute of Physical Chemistry, RWTH Aachen University, Aachen, Germany

3. Nicole Maser Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry RWTH Aachen University Aachen Germany

   Institute of Physical Chemistry, RWTH Aachen University, Aachen, Germany

4. Arne Lüchow corresponding Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry RWTH Aachen University Aachen Germany

   Institute of Physical Chemistry, RWTH Aachen University, Aachen, Germany