IN DEFENSE OF THE USE OF ATOMIC ORBITAL CONFIGURATION WAVE FUNCTIONS FOR SMALL MOLECULES1

1962 ◽  
Vol 66 (12) ◽  
pp. 2332-2333 ◽  
Author(s):  
F. A. Matsen ◽  
J. C. Browne
Keyword(s):  
Atomic Orbital ◽  
Wave Functions ◽  
Orbital Configuration

Increased Valence or Electronic Hypervalence for Symmetrical Three-Centre Molecular Orbital Configurations

2007 ◽  
Vol 60 (9) ◽  
pp. 691 ◽  
Author(s):  
Richard D. Harcourt
Keyword(s):  
Molecular Orbital ◽  
Atomic Orbital ◽  
Additional Contribution ◽  
Electron Configuration ◽  
Electron Charge ◽  
Atomic Orbitals ◽  
Maximum Value ◽  
Orbital Configuration ◽  
The One ◽  
Increased Valence

With ψ1 = y + k1a + b, ψ2 = y – b, and ψ3 = y – k3a + b as Y–A and A–B bonding, non-bonding, and antibonding three-centre molecular orbitals for a symmetrical Y–A–B type bonding unit with overlapping atomic orbitals y, a, and b, it is deduced that the maximum value for the A atom valence, (VA = Vab + Vay), is (a) 4(3 – 2√2) = 0.6863 for the one-electron and five-electron configurations Φ(1) = (ψ1)1 and Φ(5) = (ψ1)2ψ2)2(ψ3)1; (b) 8(3 – 2√2) = 1.3726 for the two-electron and four-electron configurations Φ(2) = (ψ1)2 and Φ(4) = (ψ1)2(ψ2)2; and (c) 4/3 for the three-electron configuration Φ(3) = (ψ1)2(ψ2)1. Thus for each of the three-centre molecular orbital configurations, the A-atom can exhibit increased valence, or electronic hypervalence, relative to the valence for an A-atom in a two-centre molecular orbital configuration. When k1 ≠ 0 for Φ(1) and k3 ≠ 0 for Φ(5), the A-atom odd-electron charge is not equal to zero. This odd-electron charge is available for (fractional) electron-pair bonding to a fourth atom X, to give an additional contribution, Va, to the valence. The resulting maximum value for the A-atom valence (VA = Vab + Vay + Va) is equal to 1.2020 for each of Φ(1) and Φ(5). A-atom valencies are calculated for the three-centre bonding units for several molecules and ions. The expressions for VA = Vab + Vay were derived with atomic orbital overlap integrals omitted. The present paper shows how the theory is modified when these integrals are included.

Optimum atomic orbital exponents for molecular wave functions

1970 ◽  
Vol 18 (4) ◽  
pp. 533-543 ◽  
Author(s):  
C.L. Silk ◽  
J.N. Murrell
Keyword(s):  
Atomic Orbital ◽  
Wave Functions ◽  
Orbital Exponents

Valence Bond Structures for the N3- Anion, the N3 Radical and the N6- Radical Anion

2012 ◽  
Vol 67 (9) ◽  
pp. 935-943 ◽  
Author(s):  
Richard D. Harcourta ◽  
Thomas M. Klapötke
Keyword(s):  
Radical Anion ◽  
Electron Pair ◽  
Atomic Orbital ◽  
Valence Bond ◽  
Wave Functions ◽  
The One ◽  
Lewis Structures ◽  
Increased Valence ◽  
Polarity Parameters

With Heitler-London atomic orbital-type formulations of the wave functions for (fractional) electron-pair πx(NN) and πy(NN) bonds, increased-valence structures for the N3- anion and N3- radical are equivalent to resonance between familiar standard Lewis structures and singlet diradical (or “long-bond”) Lewis structures. Theory is developed for the calculation of the polarity parameters that are associated with the one-electron πx(NN) and πy(NN) bonds in the increased-valence structures, and illustrative STO-6G estimates of their values are reported. They show that the πx and πy electrons of these bonds are strongly charge-correlated relative to each other. The increased-valence structures for the N3- anion and the N3- radical are used to help construct increased-valence structures for the N6- radical anion with C2h symmetry

scholarly journals High Harmonic Generation and the Role of Atomic Orbital Wave Functions

2007 ◽  
Vol 98 (18) ◽  
Author(s):  
J. Levesque ◽  
D. Zeidler ◽  
J. P. Marangos ◽  
P. B. Corkum ◽  
D. M. Villeneuve
Keyword(s):  
Harmonic Generation ◽  
Atomic Orbital ◽  
High Harmonic ◽  
High Harmonic Generation ◽  
Wave Functions
Sign in / Sign up

Export Citation Format

Share Document