Investigation of the distinction between van der Waals interaction and chemical bonding based on the PAEM‐MO diagram

In recent years, the basic problem of understanding chemical bonding, nonbonded, and/or van der Waals interactions has been intensively debated in terms of various theoretical methods. We propose and construct the potential acting on one electron in a molecule‐molecular orbital (PAEM‐MO) diagram, which draws the PAEM inserted the MO energy levels with their major atomic orbital components. PAEM‐MO diagram is able to show clear distinction of chemical bonding from nonbonded and/or vdW interactions. The rule for this is as follows. Along the line connecting two atoms in a molecule or a complex, the existence of chemical bonding between these two atoms needs to satisfy two conditions: (a) a critical point of PAEM exists and (b) PAEM barrier between the two atoms is lower in energy than the occupied major valence‐shell bonding MO which contains in‐phase atomic components (positive overlap) of the two considered atoms. In contrast to the chemical bonding, for a nonbonded interaction or van der Waals interaction between two atoms, both conditions (a) and (b) do not be satisfied at the same time. This is demonstrated and discussed by various typical cases, particularly those related to helium atom and HH bonding in phenanthrene. There are helium bonds in HHeF and HeBeO molecules, whereas no HH bonding in phenanthrene. The validity and limitation for this rule is demonstrated through the investigations of the curves of the PAEM barrier top and MO energies versus the internuclear distances for He2, H2, and He2+ systems. © 2014 Wiley Periodicals, Inc.

[1]  S. Grimme,et al.  When do interacting atoms form a chemical bond? Spectroscopic measurements and theoretical analyses of dideuteriophenanthrene. , 2009, Angewandte Chemie.

[2]  Gilbert N. Lewis,et al.  Valence And The Structure Of Atoms And Molecules , 1923 .

[3]  Sason Shaik,et al.  A conversation on VB vs MO theory: a never-ending rivalry? , 2003, Accounts of chemical research.

[4]  F. Escudero,et al.  Atoms in molecules , 1982 .

[5]  Zhong-Zhi Yang,et al.  Investigation of the molecular surface area and volume: Defined and calculated by the molecular face theory , 2010, J. Comput. Chem..

[6]  G. Frenking,et al.  Chemical bonding in the inclusion complex of He in adamantane, He@adam: antithesis and complement. , 2008, Chemistry.

[7]  Philip Ball,et al.  Beyond the bond , 2011, Nature.

[8]  P Hobza,et al.  Noncovalent interactions: a challenge for experiment and theory. , 2000, Chemical reviews.

[9]  Gilbert N. Lewis,et al.  The Atom and the Molecule , 1916, Resonance.

[10]  Miquel Solà,et al.  Hydrogen-hydrogen bonding in planar biphenyl, predicted by atoms-in-molecules theory, does not exist. , 2006, Chemistry.

[11]  Zhong-Zhi Yang,et al.  Polarization and bonding of the intrinsic characteristic contours of hydrogen and fluorine atoms of forming a hydrogen fluoride molecule based on an ab initio study. , 2004, The Journal of chemical physics.

[12]  Fernando Cortés-Guzmán,et al.  Chemical bonding: From Lewis to atoms in molecules , 2007, J. Comput. Chem..

[13]  Paul L. A. Popelier,et al.  Atoms in Molecules: An Introduction , 2000 .

[14]  Henry S Rzepa,et al.  The importance of being bonded. , 2009, Nature chemistry.

[15]  Zhong-Zhi Yang,et al.  Development of a method to accurately calculate the Dpb and quickly predict the strength of a chemical bond , 2013 .

[16]  J. Černý,et al.  Non-covalent interactions in biomacromolecules. , 2007, Physical chemistry chemical physics : PCCP.

[17]  M. Pettersson,et al.  A study on stabilization of HHeF molecule upon complexation with Xe atoms , 2004 .

[18]  Zhong-Zhi Yang,et al.  The changing features of the molecular intrinsic characteristic contours of H2 molecule in the ground and first excited states calculated by an ab initio method , 2002 .

[19]  R. S. Mulliken.  Spectroscopy, molecular orbitals, and chemical bonding. , 1967, Science.

[20]  F. London,et al.  Wechselwirkung neutraler Atome und homöopolare Bindung nach der Quantenmechanik , 1927 .

[21]  A. Tachibana.  Electronic energy density in chemical reaction systems , 2001 .

[22]  E. Davidson,et al.  Evaluation of a characteristic atomic radius by an ab initio method , 1997 .

[23]  T. Takayanagi,et al.  Theoretical prediction of the lifetime of the metastable helium compound: HHeF , 2002 .

[24]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[25]  W. Schwarz,et al.  Observations and descriptions versus explanations--an example: does nature, does theory know about steric hindrance? , 2012, Chemistry.

[26]  G. Scuseria,et al.  Gaussian 03, Revision E.01. , 2007 .

[27]  Werner Kutzelnigg,et al.  What I like about Hückel theory , 2007, J. Comput. Chem..

[28]  Jessica Schulze,et al.  The Nature Of The Chemical Bond , 2016 .

[29]  Zhong-Zhi Yang,et al.  Theory on the molecular characteristic contour (II) —— Molecular intrinsic characteristic contours of several typical organic molecules , 2005 .

[30]  Andreas Savin,et al.  ELF: The Electron Localization Function , 1997 .

[31]  Zhong-Zhi Yang,et al.  Method and algorithm of obtaining the molecular intrinsic characteristic contours (MICCs) of organic molecules , 2005, J. Comput. Chem..

[32]  Zhong-Zhi Yang,et al.  The molecular intrinsic characteristic contours (MICCs) of some small organic molecules , 2003 .

[33]  J. Collins,et al.  Are there neutral helium compounds which are stable in their ground state?: A theoretical investigation of HeBCH and HeBeO , 1986 .

[34]  A. Faessler,et al.  Quasi-elastic electroproduction of charged $ \rho$ -mesons on nucleons , 2010 .

[35]  Zhong-Zhi Yang,et al.  Insight into markovnikov reactions of alkenes in terms of ab initio and molecular face theory. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[36]  Zhong-Zhi Yang,et al.  STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTIONS AT CARBON (SN2(C)) AND SILICON (SN2(Si)) IN TERMS OF AB INITIO, POTENTIAL, ACTING ON AN ELECTRON IN A MOLECULE AND MOLECULAR FACE THEORY , 2009 .

[37]  W. Schwarz.  Chemical bonding: state of the art in conceptual quantum chemistry An introduction , 2001 .

[38]  Chérif F Matta,et al.  Hydrogen-hydrogen bonding: a stabilizing interaction in molecules and crystals. , 2003, Chemistry.

[39]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[40]  Klaus Ruedenberg,et al.  The Physical Nature of the Chemical Bond , 1962 .

[41]  D. Wolstenholme,et al.  Experimental and theoretical electron density study of a highly twisted polycyclic aromatic hydrocarbon: 4-methyl-[4]helicene. , 2007, The journal of physical chemistry. A.

[42]  Martin Kaupp,et al.  The role of radial nodes of atomic orbitals for chemical bonding and the periodic table , 2007, J. Comput. Chem..

[43]  I. Mayer,et al.  Bond order and valence indices: A personal account , 2007, J. Comput. Chem..

[44]  Satoko Hayashi,et al.  Atoms-in-molecules dual parameter analysis of weak to strong interactions: behaviors of electronic energy densities versus Laplacian of electron densities at bond critical points. , 2008, The journal of physical chemistry. A.

[45]  Deepak Chopra,et al.  Advances in understanding of chemical bonding: inputs from experimental and theoretical charge density analysis. , 2012, The journal of physical chemistry. A.

[46]  R. Bader,et al.  Bond paths are not chemical bonds. , 2009, The journal of physical chemistry. A.

[47]  Zhong-Zhi Yang,et al.  THE CHARACTERISTIC BOUNDARY RADII OF ATOMS , 2005 .

[48]  Paul L. A. Popelier,et al.  Atoms in molecules , 2000 .

[49]  Gernot Frenking,et al.  Unicorns in the world of chemical bonding models , 2007, J. Comput. Chem..

[50]  C. E. Dykstra,et al.  Experimental and theoretical challenges in the chemistry of noncovalent intermolecular interaction and clustering , 2000 .

[51]  Roald Hoffmann,et al.  Interaction of orbitals through space and through bonds , 1971 .

[52]  R. S. Mulliken.  Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I , 1955 .

[53]  D. Cremer,et al.  Helium chemistry: theoretical predictions and experimental challenge , 1987 .