PMID- 16967983
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20070821
LR  - 20060913
IS  - 0002-7863 (Print)
IS  - 0002-7863 (Linking)
VI  - 128
IP  - 37
DP  - 2006 Sep 20
TI  - Born-Haber-Fajans cycle generalized: linear energy relation between molecules, 
      crystals, and metals.
PG  - 12314-21
AB  - Classical procedures to calculate ion-based lattice potential energies (U(POT)) 
      assume formal integral charges on the structural units; consequently, poor 
      results are anticipated when significant covalency is present. To generalize the 
      procedures beyond strictly ionic solids, a method is needed for calculating (i) 
      physically reasonable partial charges, delta, and (ii) well-defined and 
      consistent asymptotic reference energies corresponding to the separated 
      structural components. The problem is here treated for groups 1 and 11 
      monohalides and monohydrides, and for the alkali metal elements (with their 
      metallic bonds), by using the valence-state atoms-in-molecules (VSAM) model of 
      von Szentpaly et al. (J. Phys. Chem. A 2001, 105, 9467). In this model, the 
      Born-Haber-Fajans reference energy, U(POT), of free ions, M(+) and Y(-), is 
      replaced by the energy of charged dissociation products, M(delta)(+) and 
      Y(delta)(-), of equalized electronegativity. The partial atomic charge is 
      obtained via the iso-electronegativity principle, and the asymptotic energy 
      reference of separated free ions is lowered by the "ion demotion energy", IDE = 
      -(1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)), where delta(VS) is the valence-state 
      partial charge and (I(VS,M) - A(VS,Y)) is the difference between the 
      valence-state ionization potential and electron affinity of the M and Y atoms 
      producing the charged species. A very close linear relation (R = 0.994) is found 
      between the molecular valence-state dissociation energy, D(VS), of the VSAM 
      model, and our valence-state-based lattice potential energy, U(VS) = U(POT) - 
      (1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)) = 1.230D(VS) + 86.4 kJ mol(-)(1). 
      Predictions are given for the lattice energy of AuF, the coinage metal 
      monohydrides, and the molecular dissociation energy, D(e), of AuI. The coinage 
      metals (Cu, Ag, and Au) do not fit into this linear regression because d orbitals 
      are strongly involved in their metallic bonding, while s orbitals dominate their 
      homonuclear molecular bonding.
FAU - Glasser, Leslie
AU  - Glasser L
AD  - Nanochemistry Research Institute, Department of Applied Chemistry, Curtin 
      University of Technology, GPO Box U1987, Perth, Western Australia 6845, 
      Australia. l.glasser@exchange.curtin.edu.au
FAU - von Szentpaly, Laszlo
AU  - von Szentpaly L
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
EDAT- 2006/09/14 09:00
MHDA- 2006/09/14 09:01
CRDT- 2006/09/14 09:00
PHST- 2006/09/14 09:00 [pubmed]
PHST- 2006/09/14 09:01 [medline]
PHST- 2006/09/14 09:00 [entrez]
AID - 10.1021/ja063812p [doi]
PST - ppublish
SO  - J Am Chem Soc. 2006 Sep 20;128(37):12314-21. doi: 10.1021/ja063812p.