Calculation of molecular one-electron properties using coupled Hartree-Fock methods

Thomsen, K.; Swanstrøm, Peter

doi:10.1080/00268977300102061

Cited by 48 publications

(14 citation statements)

References 33 publications

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“…Components of both molecules are given for comparison in the O -H bond axis framework. Susceptibilities of HoO calculated with basis set I are comparable with those of Thomsen and Sw r anstrom 6 calculated with the near Hartree-Fock basis set without gauge invariant orbitals. STO-3G basis set gives about 20% too small absolute values as was noticed before 2 .…”

supporting

confidence: 64%

Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Žaucer

Pumpernik

Hladnik

et al. 1976

Zeitschrift Für Naturforschung A

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supporting

confidence: 64%

Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Žaucer

Pumpernik

Hladnik

et al. 1976

Zeitschrift Für Naturforschung A

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“…It is obvious that such analytic calculations can hardly be performed for larger basis sets, especially those involving higher GTOS. A similar bottleneck of analytic perturbation calculations with variable bases has already been pointed out by Thomsen and Swanstrom [20] in their computations of molecular force constants. The same problem appears also in the case of the so-called gauge invariant atomic bases [21] as well as for the variable-gauge orbitals [2].…”

Section: -(P"'*/2d2)[e(+d +D/p'")+e(-d -D/p('')-2e(o O)] (41)mentioning

confidence: 88%

“…where R(') is the self-consistent unperturbed density matrix in the nonorthogonal basis set, R(') denotes the corresponding SCF first-order density matrix, and the matrices of the form G(R, g) are defined by with g being the supermatrix of two-electron integrals (20) in a given basis set. The HF Hamiltonian matrix h = h(R)…”

Section: (')R(n)h(")-h(o)r(o)s(')]r(')mentioning

confidence: 99%

Variable basis sets in perturbation theory: Numerical finite perturbation versus analytic approach

Epstein

Sadlej

1979

Int J of Quantum Chemistry

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AbstractsWe consider the problem of determining variational, external-field-dependent corrections to nonoptimal zero-field nonlinear parameters. Both a direct analytic perturbation analysis and finite perturbation methods are described in a general way and in detail for the SCF approximation. The abstract theory is illustrated by reference to the results of several explicit calculations. Also, the sensitivity of the results to the choice of zero-field values is discussed.Nous considirons le problkme de dkterminer des corrections variationnelles dkpendantes d'un champ exttrieur a des paramktres non-liniaires, non-optimalisks au champ nul. Nous dkcrivons une analyse perturbationnelle analytique directe et des mithodes de perturbations finies d'une facon gknirale et en dttail pour I'approximation SCF. La thkorie abstraite est illustrte par les risultats de plusieurs calculs explicites. Nous discutons aussi la sensibititk des risultats par rapport aux choix des valeurs correspondantes au champ nul.wir betrachten das problem von einem ausseren Feld abhangige Variationskorrekture zu nichtoptimalen, nicht-linearen Nullfeldparametern zu bestimmen. Sowohl eine direkte analytische Storungsanalyse als auch endliche Storungsmethoden werden in einer allgemeinen Weise und in Einzelheiten fur die SCF-Naherung beschrieben. Die abstrakte Theorie wird mit den Ergebnissen von mehreren expliziten Berechnungen illustriert. Auch die Empfindlichkeit der Resultate mit Rucksicht auf die Wahl von Nullfeldwerten wird diskutiert.

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“…For closed shell molecules without near-degeneracies CHF polarizabilities account for approximately 90 per cent of the experimental values [1]. Table 3 contains calculated CHF polarizabilities for water molecule selected from the literature [1,[47][48][49][50][51][52][53][54] and also includes the number of basis functions used in each calculation. From the results in this table it is apparent that the choice of basis functions is a crucial factor in evaluating accurate CHF polarizabilities.…”

Section: Finite-field Perturbation Methodsmentioning

confidence: 99%

Finite-field calculations of molecular polarizabilities using field-induced polarization functions: second- and third-order perturbation correlation corrections to the coupled Hartree-Fock polarizability of H₂O

et al. 1979

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Ordinary Rayleigh-Schr6dinger perturbation theory with Moller-Plesset (RSMP) partitioning is used to calculate second-and third-order correlation corrections to the CHF polarizability and dipole moment of the water molecule by a finite-field procedure. [2/1] Pad6 approximants are found to be useful in accelerating the convergence of the property perturbation expansions. Field-induced polarization functions suitable for polarizability calculations are determined. The average polarizability calculated, neglecting vibrational averaging, with Dunning's (9s5p/4s-4s2p/2s) contracted GTO basis set augmented by field-induced lslp2d/lp polarization functions is within 3 per cent of the experimental result. Correlation corrections to the dipole moment and polarizability of the water molecule calculated by the finite-field RSMP and single+double excitation CI(SDCI) methods for the same basis set are found to be in close agreement. The RSMP approach has the advantages of being size-consistent and of being capable of greater efficiency than the SCDI method. Comparative calculations carried out using EpsteinNesbet partitioning show that through third order RSEN correlation perturbation expansions for the dipole moment and polarizability are less rapidly convergent than RSMP expansions. However, reasonable accord with RSMP results can be achieved by using [2/1] Pad6 approximants to accelerate the convergence of RSEN energy perturbation expansions. The convergence of RSMP property correlation expansions based on the zeroth-order uncoupled-Hartree-Fock (UCHF) and coupled-Hartree-Fock (CHF) approximations are compared through third order. Whereas the CHF + RSMP expansions are for practical purposes fully converged, the UCHF+RSMP expansions are not adequately converged.

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Calculation of molecular one-electron properties using coupled Hartree-Fock methods

Cited by 48 publications

References 33 publications

Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Variable basis sets in perturbation theory: Numerical finite perturbation versus analytic approach

Finite-field calculations of molecular polarizabilities using field-induced polarization functions: second- and third-order perturbation correlation corrections to the coupled Hartree-Fock polarizability of H₂O

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Calculation of molecular one-electron properties using coupled Hartree-Fock methods

Cited by 48 publications

References 33 publications

Calculation of Magnetic Shielding and Susceptibility of H2O and FOH with Gauge Invariant Gaussian Basis Set

Calculation of Magnetic Shielding and Susceptibility of H2O and FOH with Gauge Invariant Gaussian Basis Set

Variable basis sets in perturbation theory: Numerical finite perturbation versus analytic approach

Finite-field calculations of molecular polarizabilities using field-induced polarization functions: second- and third-order perturbation correlation corrections to the coupled Hartree-Fock polarizability of H2O

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Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Calculation of Magnetic Shielding and Susceptibility of H₂O and FOH with Gauge Invariant Gaussian Basis Set

Finite-field calculations of molecular polarizabilities using field-induced polarization functions: second- and third-order perturbation correlation corrections to the coupled Hartree-Fock polarizability of H₂O