Mathematical modeling and physical reality in noncovalent interactions

被引:196
作者
Politzer, Peter [1 ,2 ]
Murray, Jane S. [1 ,2 ]
Clark, Timothy [3 ,4 ]
机构
[1] Univ New Orleans, Dept Chem, New Orleans, LA 71048 USA
[2] CleveTheoComp, Cleveland, OH 44113 USA
[3] Univ Erlangen Nurnberg, Dept Chem & Pharm, Comp Chem Ctr, D-91052 Erlangen, Germany
[4] Univ Portsmouth, Ctr Mol Design, Portsmouth PO1 2DY, Hants, England
关键词
Noncovalent interactions; Hellmann-Feynman theorem; Electrostatic potential; Polarization; Charge transfer; Dispersion; sigma-hole interactions; Halogen bonding; Hydrogen bonding; HELLMANN-FEYNMAN THEOREM; HALOGEN; FORCES; ATOMS; BOND; VAN; MOLECULES; BEHAVIOR;
D O I
10.1007/s00894-015-2585-5
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The Hellmann-Feynman theorem provides a straightforward interpretation of noncovalent bonding in terms of Coulombic interactions, which encompass polarization (and accordingly include dispersion). Exchange, Pauli repulsion, orbitals, etc., are part of the mathematics of obtaining the system's wave function and subsequently its electronic density. They do not correspond to physical forces. Charge transfer, in the context of noncovalent interactions, is equivalent to polarization. The key point is that mathematical models must not be confused with physical reality.
引用
收藏
页数:10
相关论文
共 61 条
[1]   Defining the hydrogen bond: An account (IUPAC Technical Report) [J].
Arunan, Elangannan ;
Desiraju, Gautam R. ;
Klein, Roger A. ;
Sadlej, Joanna ;
Scheiner, Steve ;
Alkorta, Ibon ;
Clary, David C. ;
Crabtree, Robert H. ;
Dannenberg, Joseph J. ;
Hobza, Pavel ;
Kjaergaard, Henrik G. ;
Legon, Anthony C. ;
Mennucci, Benedetta ;
Nesbitt, David J. .
PURE AND APPLIED CHEMISTRY, 2011, 83 (08) :1619-1636
[2]   Useful lower limits to polarization contributions to intermolecular interactions using a minimal basis of localized orthogonal orbitals: Theory and analysis of the water dimer [J].
Azar, R. Julian ;
Horn, Paul Richard ;
Sundstrom, Eric Jon ;
Head-Gordon, Martin .
JOURNAL OF CHEMICAL PHYSICS, 2013, 138 (08)
[3]   Pauli repulsions exist only in the eye of the beholder [J].
Bader, RFW .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (10) :2896-2901
[4]   PROPERTIES OF ATOMS IN MOLECULES - ATOMIC VOLUMES [J].
BADER, RFW ;
CARROLL, MT ;
CHEESEMAN, JR ;
CHANG, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (26) :7968-7979
[5]  
Bader RFW., 1968, CAN J CHEM, V46, P953, DOI DOI 10.1139/V68-157
[6]   BINDING REGIONS IN DIATOMIC MOLECULES [J].
BERLIN, T .
JOURNAL OF CHEMICAL PHYSICS, 1951, 19 (02) :208-213
[7]   VAN DER WAALS VOLUMES + RADII [J].
BONDI, A .
JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (03) :441-+
[8]   Correct electrostatic treatment of noncovalent interactions: the importance of polarization [J].
Clark, Timothy ;
Politzer, Peter ;
Murray, Jane S. .
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2015, 5 (02) :169-177
[9]   Role of Polarization in Halogen Bonds [J].
Clark, Timothy ;
Murray, Jane S. ;
Politzer, Peter .
AUSTRALIAN JOURNAL OF CHEMISTRY, 2014, 67 (03) :451-456
[10]  
Deb B.M., 1981, Force concept in chemistry