Transferability of the electronic structure characteristics of saturated molecules

Gineitytė, V.; Shatkovskaya, D. B.

doi:10.1002/qua.560390104

Cited by 18 publications

(5 citation statements)

References 6 publications

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“…(The generalized solution has been accordingly expressed in terms of entire blocks of both Hamiltonian and overlap matrices.) Finally, a direct way of obtaining the DM based on solution of the so-called commutation equation has been applied in the first derivations of this matrix [18][19][20][21][22][23][24]. These results will also be discussed briefly in Sections 4.1 and 4.2.…”

Section: Non-commutative Rspt In the Framework Of The Non-canonical Mmentioning

confidence: 99%

“…As a result, a Hamiltonian matrix consisting of four submatrices like that of Section 4.1 has been constructed. The first-order magnitude of interactions (resonance parameters) of the intersubset type (i. e. between a BBO and an ABO) versus the intersubset energy gaps [24] follows from the relevant estimations [19,21,[75][76][77][78][79]. These ratios between matrix elements, in turn, imply applicability to both alkanes and their derivatives of the NCRSPT and thereby of the results of Section 4.…”

Section: Interbond Interaction In Alkanes and Their Derivativesmentioning

confidence: 99%

“…Developement of this theory started with its particular cases devoted to the common quantum-mechanical description of saturated molecules [18][19][20][21][22][23][24]. (Note that entire classes of the so-called related compounds usually are studied in the classical chemistry instead of individual molecules.)…”

Section: Introductionmentioning

confidence: 99%

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Non-commutative Rayleigh-Schrödinger perturbation theory and its applications in quantum chemistry

Gineitytė¹

2004

Lith. J. Phys.

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The review is devoted to developement and applications of the so-called non-commutative Rayleigh-Schrödinger perturbation theory (NCRSPT). As opposed to the standard RSPT used for taking into account weak interorbital interactions, the NCRSPT is aimed to account for weak interactions inside and between entire subsets of basis functions of arbitrary dimensions separated by substantial energy gaps. Accordingly, this new PT is formulated in terms of multidimensional (non-commutative) quantities, including row-matrices of basis functions corresponding to individual subsets and the so-called eigenblocks playing the role of eigenvalues. When discussing applications, the principal attention is paid to the perturbative version of the non-canonical theory of molecular orbitals based on the Brillouin theorem.

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Section: Non-commutative Rspt In the Framework Of The Non-canonical Mmentioning

confidence: 99%

Section: Interbond Interaction In Alkanes and Their Derivativesmentioning

confidence: 99%

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Non-commutative Rayleigh-Schrödinger perturbation theory and its applications in quantum chemistry

Gineitytė¹

2004

Lith. J. Phys.

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“…The term "saturated organic molecules" used throughout this article embraces systems containing more or less localized two-centre chemical bonds and lone electron pairs. The more precise definition consists in the first-order magnitude of the nonneighbouring resonance parameters versus those between strongly-overlapping (neighbouring) pairs of orbitals [13,[27][28][29][30][31][32] in the initial basis of 1s H AOs of hydrogen atoms and sp 3 -hybrid AOs (HAOs) of the remaining atoms. For simplicity let us call them both the HAO basis.…”

Section: One-electron Density Matrix Of Saturated Organic Molecules Imentioning

confidence: 99%

Intrabond effects caused by interbond interaction in saturated organic molecules

Gineitytė¹

2005

Lith. J. Phys.

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The paper is devoted to further developement of the perturbative version of the noncanonical method of molecular orbitals overviewed recently [V. Gineitytė, Lithuanian J. Phys. 44, 219 (2004)] and called the PNCMO theory. General expressions are derived for the common one-electron density matrix of saturated organic molecules in the basis of 1sH AOs of hydrogen atoms and sp 3 -hybrid AOs of the remaining atoms and for respective total energies. Explicit algebraic representations are obtained for intrabond effects taking place in the above-specified systems due to interbond interaction. The concepts of homolytic and heterolytic predissociation of bonds are introduced to describe these effects. Interdependences are demonstrated between increments of various intra-and interbond effects to the total energy of the systems under study. Moreover, the final stabilization energy of the system versus the respective set of isolated bonds and lone electron pairs is shown to result from a certain "balance" between increments of opposite signs. In particular, the stabilizing contributions of newly-formed bond orders between orbitals of different bonds due to their interaction are shown to be necessarily accompanied by destabilizing increments of intrabond type that are traced back to the homo-and heterolytic predissociation of bonds. The results obtained are compared to those of particular cases studied previously.

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“…Therefore, to give theoretical justification for the mentioned empirical schemes and expose their relation with local structure of saturated compounds, we resorted to the approach successfully used in the study of common properties of Š ATKOVSKIENĖ electron density distribution in tetrahedral systems [7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Theoretical justification of empirical additivity schemes for conformational energies

Šatkovskienė

2002

Int J of Quantum Chemistry

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Additivity of conformational energy of saturated molecules has been studied using the perturbation theory for density matrix. Analytical expressions for both total and conformational energies have been obtained and analyzed up to the third-order members. It is shown that the conformational energy of compounds under investigation can be presented as a sum of transferable increments corresponding to the energies of separate conformational segments and their sequences. The role of end groups in determination of energies of conformational segments is revealed. The influence of substitution has been investigated. The dependence of subtle conformational effects on common structural peculiarities of Hamiltonians of saturated molecules has been concluded.

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Transferability of the electronic structure characteristics of saturated molecules

Cited by 18 publications

References 6 publications

Non-commutative Rayleigh-Schrödinger perturbation theory and its applications in quantum chemistry

Non-commutative Rayleigh-Schrödinger perturbation theory and its applications in quantum chemistry

Intrabond effects caused by interbond interaction in saturated organic molecules

Theoretical justification of empirical additivity schemes for conformational energies

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