Regularities in the behavior of dipole moment functions of diatomic molecules at very small internuclear separations

Buldakov, Michail A.; Koryukina, E. V.; Cherepanov, Victor N.; Kalugina, Yulia N.

doi:10.1103/physreva.78.032516

Cited by 9 publications

(18 citation statements)

References 32 publications

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“…This leads to the reversal in energy order and the consequent level crossing of two diabatic states, because He + ‐H ‐ is more stable than He ‐ ‐H + . This explanation is supported by the formula for DMCs at small R given by Buldakov et al ., where the leading term of the DMCs is R 3 so that μ ( R ) ≈ A nlλ R 3 . The coefficients A nlλ , calculated using Fischer's Hartree‐Fock program, are in good agreement with the diabatic DMCs for the nsσ , npσ , and npπ series, thus they support the reversal of the dipole moments at the avoided crossing points.…”

Section: Resultssupporting

confidence: 59%

“…If the Hartree‐Fock approximation is used for the states of the UA, then only the

n l^{n_{1}} \to n l^{n_{1} - 1} n^{'} l^{'}

atomic transitions should be included in the summation. Buldakov et al . derived the formula for this case.…”

Section: Behaviors Of Dmcs At Small Rmentioning

confidence: 99%

“…The problem with Bingel's theory was pointed out by Levine and corrected by Byers‐Brown using the cusp condition for wavefunctions at the origin. The general theory of dipole moments at small R using Bingel's method was also developed by Buldakov et al . As far as we know, these methods have only been applied to a few of the lowest states in several molecules.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Study of 15 Singlet Rydberg Series of HeH and Their Correlation with the Rydberg Series of Li

Kim

Lee

2016

Bulletin Korean Chem Soc

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We theoretically study 37 Rydberg states of HeH derivable from the He(1s 2) + H(nl) configuration with n ≤ 5 along with three states with n = 6. The multireference configuration interaction method is used to calculate their electronic energy curves (EECs) for the internuclear distance R from 0 to 28a 0, which are regarded as the united‐atom (UA) and separated‐atoms (SA) limits, respectively. The 15 Rydberg series (nsσ, npσ, ndσ, nfσ, ngσ, ndδ, nfδ, ngδ, ngγ, npπ, ndπ, nfπ, ngπ, nfϕ, and ngϕ) are identified. Bingel's perturbation theory is used to explain the role of the core part and the Rydberg orbitals in the behavior of EECs at small R. Smith's theory of diabatization is directly solved to obtain the diabatic quantum defect curves (QDCs). From the correlations in diabatic QDCs between the UA and SA limits, the following order of orbital energies in the equilibrium region is found: npσ < nsσ < npπ < ndσ < ndπ < nfσ < nfπ < nfδ < nfϕ < ndδ, except 5dδ < 5fϕ. This order is identical to that in one‐electron molecular systems at small R, except for the nsσ and npπ series. The correlation rules are n UA = n SA + 1 for the npσ series and n UA = n SA for other series; additionally, l UA = l SA for all cases except for the 2pσ − σ1s correlation. A reversal of the diabatic dipole moment at avoided crossing points of the nsσ and npσ series is observed, and explained by the behaviors of ns and np wavefunctions of H at small R.

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Section: Resultssupporting

confidence: 59%

“…If the Hartree‐Fock approximation is used for the states of the UA, then only the

n l^{n_{1}} \to n l^{n_{1} - 1} n^{'} l^{'}

atomic transitions should be included in the summation. Buldakov et al . derived the formula for this case.…”

Section: Behaviors Of Dmcs At Small Rmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Study of 15 Singlet Rydberg Series of HeH and Their Correlation with the Rydberg Series of Li

Kim

Lee

2016

Bulletin Korean Chem Soc

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“…To allow for the probing of higher-lying vibrational states, some such studies have attempted to construct appropriate dipole and quadrupole moment functions over a broad range of internuclear distances r by combining limited experimental data with reliable ab initio approximants. The resulting functions, obtained either as Padé approximants or as piecewise-continuous functions, − exhibit physically correct shapes at small and large internuclear separations and closely coincide with genuine dipole and quadrupole moment and polarizability functions in the equilibrium region. However, although contemporary theory provides the sought-after radial functions quite accurately (see, e.g., refs − ), it may still not provide results with experimentally achievable accuracy (see, e.g., refs − ).…”

Section: Introductionmentioning

confidence: 67%

Reduced Radial Curves of Diatomic Molecules

Špirko

2023

J. Chem. Theory Comput.

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The prospect of using the concept of a universal reduced potential energy curve (RPC) for a broader class of radial molecular functions is explored by performing appropriate model calculations for the electric dipole moment functions of the hydrogen halides HF, HCl, and HBr. The reduced radial functions of the model systems, constructed from their best available theoretical approximants, coincide so closely that they can be used as few-parameter universal representations of functions available in the literature. Given the mathematical nature of the problem addressed here, the results are not limited to the functions studied but can be applied equally well to all radial molecular functions that have similar shapes, such as electric quadrupole moment and dipole polarizability functions.

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“…At present, there are only a few works where ab initio calculations of the dipole moment functions of diatomic many-electron molecules have been performed at small internuclear separations R [5-8, 21, 22]. However, only three works [21][22][23] deal with the investigation of the regularities in the behaviour of the functions μ(R) at R → 0. In [23], only qualitative R-dependences of the function μ(R) at R → 0 were shown, but this work gives neither calculation schemes nor numerical results for μ(R).…”

Section: Introductionmentioning

confidence: 99%

Periodic law for the dipole moment functions of diatomic molecules at small internuclear distances

Buldakov

Cherepanov

Koryukina

2009

J. Phys. B: At. Mol. Opt. Phys.

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Regularities in the behavior of dipole moment functions of diatomic molecules at very small internuclear separations

Cited by 9 publications

References 32 publications

A Study of 15 Singlet Rydberg Series of HeH and Their Correlation with the Rydberg Series of Li

A Study of 15 Singlet Rydberg Series of HeH and Their Correlation with the Rydberg Series of Li

Reduced Radial Curves of Diatomic Molecules

Periodic law for the dipole moment functions of diatomic molecules at small internuclear distances

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