Molecular polarizability in quantum defect theory: polar molecules

Akindinova, E. V.; Chernov, V. E.; Kretinin, I. Yu.; Zon, B. A.

doi:10.1103/physreva.81.042517

Cited by 14 publications

(9 citation statements)

References 52 publications

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“…The values of the parallel α el and perpendicular α ⊥ el electronic polarizabilities for the molecules under inspection are presented in Ref. [22].…”

Section: Numerical Resultsmentioning

confidence: 99%

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Screening and enhancement of an oscillating electric field in molecules

2019

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According to the Schiff theorem, the atomic electrons completely screen the atomic nucleus from an external static electric field. However, this is not the case if the field is time-dependent. Electronic orbitals in atoms either shield the nucleus from an oscillating electric field when the frequency of the field is off the atomic resonances or enhance this field when its frequency approaches an atomic transition energy. In molecules, not only electronic, but also rotational and vibrational states are responsible for the screening of oscillating electric fields. As will be shown in this paper, the screening of a low-frequency field inside molecules is much weaker than it appears in atoms owing to the molecular ro-vibrational states. We systematically study the screening of oscillating electric fields inside diatomic molecules in different frequency regimes,i.e., when the field's frequency is either of order of ro-vibrational or electronic transition frequencies. In the resonance case, we demonstrate that the microwave-frequency electric field may be enhanced up to six orders in magnitude due to rovibrational states. We also derive the general formulae for the screening and resonance enhancement of oscillating electric field in polyatomic molecules. Possible applications of these results include nuclear electric dipole moment measurements and stimulation of nuclear reactions by laser light.

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“…The values of the parallel α el and perpendicular α ⊥ el electronic polarizabilities for the molecules under inspection are presented in Ref. [22].…”

Section: Numerical Resultsmentioning

confidence: 99%

“…The value of ω e may be found in the NIST database [21]) while the electronic-range frequency ω el is available in Ref. [22].…”

Section: Numerical Resultsmentioning

confidence: 99%

Screening and enhancement of an oscillating electric field in molecules

2019

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“…Neutral CaF is regarded as a Rydberg molecule even down to its ground state, and as a result, the outer electron is molecular in character, not atomic. The CaF polarizability anisotropy is strongly negative, 36,114 ∆α/ᾱ = −0.6 due to the fact that the unpaired electron is back-polarized, residing behind the metal ion which resists pulling the electron away along the axis. An atoms-in-molecules approach is not useful for covalent or electrically diffuse systems.…”

Section: Example: Potential Of Neutral Hfmentioning

confidence: 99%

“…33 Frequency dependent polarizability is important at frequencies approaching electronic transitions. [34][35][36] Because there are no retardation effects when the point charge is moving much slower than the core electrons, we provisionally omit those terms and focus on approximations for electric properties of molecular ions which are ionic in character and amenable to an atoms-in-molecule approach. This work develops effective potentials that can yield transferable atomic properties including polarizability quenching by Pauli repulsion and charge overlap.…”

Section: Introductionmentioning

confidence: 99%

Electric potential invariants and ions-in-molecules effective potentials for molecular Rydberg states

Coy

Grimes

Zhou

et al. 2016

The Journal of Chemical Physics

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The dependence of multipole moments and polarizabilities on external fields appears in many applications including biomolecular molecular mechanics, optical non-linearity, nanomaterial calculations, and the perturbation of spectroscopic signatures in atomic clocks. Over a wide range of distances, distributed multipole and polarizability potentials can be applied to obtain the variation of atom-centered atoms-in-molecules electric properties like bonding-quenched polarizability. For cylindrically symmetric charge distributions, we examine single-center and atom-centered effective polarization potentials in a non-relativistic approximation for Rydberg states. For ions, the multipole expansion is strongly origin-dependent, but we note that origin-independent invariants can be defined. The several families of invariants correspond to optimized representations differing by origin and number of terms. Among them, a representation at the center of dipole polarizability optimizes the accuracy of the potential with terms through 1/r. We formulate the single-center expansion in terms of polarization-modified effective multipole moments, defining a form related to the source-multipole expansion of Brink and Satchler. Atom-centered potentials are an origin independent alternative but are limited both by the properties allowed at each center and by the neglected effects like bond polarizability and charge flow. To enable comparisons between single-center effective potentials in Cartesian or spherical form and two-center effective potentials with differing levels of mutual induction between atomic centers, we give analytical expressions for the bond-length and origin-dependence of multipole and polarizability terms projected in the multipole and polarizability expansion of Buckingham. The atom-centered potentials can then be used with experimental data and ab initio calculations to estimate atoms-in-molecules properties. Some results are given for BaF and HF showing the utility and limitations of the approach. More detailed results on X Σ CaF are published separately.

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“…Due to the fact that LiH is a small molecule containing only four electrons, it constitutes an ideal system for the highly accurate calculations at different levels of theoretical approximations, including the explicitly correlated wave functions, configuration interaction (CI) as well as coupled cluster (CC) methods. The set of reference data available for this particular molecule contains, among others, the electronic and vibrational contributions to dipole moment and (hyper)polarizabilities, determined within both nonadiabatic and Born-Oppenheimer approximations [18,19,22,[73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90]. Moreover, the dipole moment of LiH in the first bonded excited state (A 1 Σ + ) is much smaller (and of the opposite sign) than that in the ground state, what indicates the presence of charge-transfer state.…”

Section: Introductionmentioning

confidence: 99%