Analysis of molecular orbital wave functions in terms of valence bond functions for molecular fragments. I. Theory

Hiberty, Philippe C.

doi:10.1002/qua.560190207

Cited by 21 publications

(6 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…37 [The interloge correlation terms reduce to effective pair populations if the explicit integration over the atomic domains is replaced by the Mulliken-like approximation of the corresponding integrals. 27 ] The close parallel with the effective pair populations is clearly seen also from the existence of the general normalization that is a straightforward counterpart of the formula (9). Based on this parallel, the F(X,Y) terms can be related to the Lewis formula in exactly the same way as the effective pair populations.…”

Section: Theoreticalmentioning

confidence: 83%

“…The relation between the effective pair populations and chemical bonds is also underlined by the normalization derived from eq 6 Another interesting property of effective pair populations is that the values of Π AB (eff) are usually very small for the pairs of atoms not connected in the classical structural formula by a bond. As a consequence, the exact normalization (9) can often be rewritten in the form (10), which can be regarded as a simple numerical test of how well the molecular structure is described by a classical Lewis formula.…”

Section: Theoreticalmentioning

confidence: 99%

“…Nevertheless, the immense debt which chemistry owes to this model stimulated and still stimulates the attempts to reconcile both alternative pictures of bonding. − If we disregard earlier studies based on the idea of localized orbitals, − the first attempt to substantiate the electron pair nature of chemical bonding theoretically is represented by the so-called loge theory. , Closely related to this theory are also more recent studies by Mel-Levy and Julg, , who proposed to identify chemical bonds with the regions of small fluctuation of electron pair. Unfortunately, these early attempts were not entirely convincing and it was even proposed to abandon the idea of chemical bonds as the basic building block of molecules …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Pair Population Analysis within AIM Theory

et al. 2000

View full text Add to dashboard Cite

The pair population analysis developed some time ago as a straightforward link between quantum chemical and classical picture of bonding was generalized by incorporating its formalism into the framework of AIM theory. A detailed numerical comparison between the results derived from the original pair population analysis and those from AIM generalization is reported. On the basis of this comparison, the reliability of both approaches is evaluated. In addition to this a numerical test of the accuracy of the Lewis electron pair model is also reported.

show abstract

Section: Theoreticalmentioning

confidence: 83%

Section: Theoreticalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Pair Population Analysis within AIM Theory

et al. 2000

View full text Add to dashboard Cite

show abstract

“…To expand a molecular orbital wave function into a VB wave function, the Hiberty and Leforestier formalism has been used [17,19]. This method is based on the fact that both V B and MO wave functions can be ultimately expanded linearly into a common set of Slater determinants formed by atomic orbitals.…”

Section: Methodsmentioning

confidence: 99%

Analysis in terms of valence‐bond structures of environmental effects on the electronic structure of molecules

Solà

Lledós

Duran

et al. 1991

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Environmental effects on the electronic structure of molecules caused by external perturbations are studied by means of an expansion of molecular orbital wave functions into valence-bond (VB) wave functions. Applications are carried out to the 7 system of butadiene, hydroxyethylene, acrolein, and carbonyl oxide and also to the full electronic system of water. The external perturbations considered are uniform electric fields, nonuniform electric fields, and reaction fields created by solvents. A different behavior is found between nonpolar and polar species in the presence of solvents. Some consequences on the behavior of molecules under the influence of the different electric fields are discussed.

show abstract

“…This problem is similar to the analysis of the molecular-orbital wave functions in terms of the valence-bond wave functions (see, e.g. , [47]}.…”

Section: Acknowledgmentmentioning

confidence: 99%

Nonadiabatic formulation of the slow-atomic-collision problem in the finite electronic basis

1994

View full text Add to dashboard Cite

The resonating-group method developed for nuclear collisions is used to obtain equations describing the collisions of slow atoms. On one hand, these equations correctly take into account the indistinguishability of electrons and scattering boundary conditions and therefore are free from the drawbacks of conventional equations in the adiabatic electronic basis. On the other hand, they retain the form of the latter equations and therefore are in agreement with the generally accepted picture of heavy-particle motion in the fields of adiabatic electronic potentials accompanied by nonadiabatic transitions. The general theory is illustrated by considering the interaction of two ground-state hydrogen atoms in the Heitler-London electronic basis.PACS number(s): 34.10.+x, 34.40.+n[6] JM= -, 'MH was taken for all internuclear distances. It is to be noted here that in [20], trying to reproduce experimental highly excited vibrational levels of H2 on the basis of the best Kolos-%olniewicz potential for the X'X+ state, the authors had to fit an effective value for the reduced mass and obtained a value very near to -, 'MH.But such a choice is incompatible with the Born-Oppenheimer picture where the nuclei are assumed to move in the fields of adiabatic electronic potentialseigenenergies of the electronic Hamiltonian for clamped nuclei to which the so-called adiabatic correction is added (see, e.g. , [13]). The reduced mass of the nuclei enters the set of coupled equations corresponding to this picture

show abstract

Analysis of molecular orbital wave functions in terms of valence bond functions for molecular fragments. I. Theory

Cited by 21 publications

References 11 publications

Pair Population Analysis within AIM Theory

Pair Population Analysis within AIM Theory

Analysis in terms of valence‐bond structures of environmental effects on the electronic structure of molecules

Nonadiabatic formulation of the slow-atomic-collision problem in the finite electronic basis

Contact Info

Product

Resources

About