scholarly journals Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

2017 ◽  
Vol 13 (9) ◽  
pp. 4063-4078 ◽  
Author(s):  
Elvira R. Sayfutyarova ◽  
Qiming Sun ◽  
Garnet Kin-Lic Chan ◽  
Gerald Knizia
Keyword(s):  
Atomic Valence

Studies on bond and atomic valences. I. correlation between bond valence and bond angles in SbIII chalcogen compounds: the influence of lone-electron pairs

1996 ◽  
Vol 52 (1) ◽  
pp. 7-15 ◽  
Author(s):  
X. Wang ◽  
F. Liebau
Keyword(s):  
Statistical Analysis ◽  
Valence State ◽  
Lone Electron Pair ◽  
Electron Pair ◽  
Bond Valence ◽  
Continuous Change ◽  
Oxidation Number ◽  
Electron Pairs ◽  
Atomic Valence ◽  
Bond Valence Parameter

In the present bond-valence concept the bond-valence parameter ro is treated as constant for a given pair of atoms, and it is assumed that the bond valence sij is a function of the corresponding bond length Dij , and that the atomic valence is an integer equal to the formal oxidation number for Vi derived from stoichiometry. However, from a statistical analysis of 76 [SbIIIS n ] and 14 [SbIIISe n ] polyhedra in experimentally determined structures, it is shown that for SbIII—X bonds (X = S, Se), ro is correlated with {\bar \alpha} i , the average of the X—Sb—X angles between the three shortest Sb—X bonds. This is interpreted as a consequence of a progressive retraction of the 5s lone-electron pair from the SbIII nucleus, which can be considered as continuous change of the actual atomic valence act Vi of Sb from +3 towards +5. A procedure is derived to calculate an effective atomic valence eff Vi of SbIII from the geometry, {\bar \alpha} i and Dij , of the [SbIII Xn ] polyhedra, which approximates act Vi and is a better description of the actual valence state of SbIII than the formal valence for Vi . Calculated eff V SbIII are found to vary between +2.88 and +3.80 v.u. for [SbIIIS n ] and between +2.98 and +3.88 v.u. for [SbIIISe n ] polyhedra. It is suggested that a corresponding modification of the present bond-valence concept is also required for other cations with lone-electron pairs.

Chemical Affinity and Atomic Valence

1919 ◽  
Vol 88 (2279supp) ◽  
pp. 154-155
Author(s):  
G. Ciamician ◽  
M. Padoa
Keyword(s):  
Chemical Affinity ◽  
Atomic Valence

A stepwise atomic, valence-molecular, and full-molecular optimisation of the Hartree–Fock/Kohn–Sham energy

2009 ◽  
Vol 11 (27) ◽  
pp. 5805 ◽  
Author(s):  
Branislav Jansík ◽  
Stinne Høst ◽  
Mikael P. Johansson ◽  
Jeppe Olsen ◽  
Poul Jørgensen ◽  
...  
Keyword(s):  
Hartree Fock ◽  
Atomic Valence

Determination of atomic valence indices from population analyses at correlated level

2003 ◽  
Vol 24 (15) ◽  
pp. 1902-1909 ◽  
Author(s):  
R. Bochicchio ◽  
L. Lain ◽  
A. Torre
Keyword(s):  
Population Analyses ◽  
Atomic Valence
Sign in / Sign up

Export Citation Format

Share Document