Fully relativistic coupled-cluster static dipole polarizabilities of the positively charged alkali ions from Li+ to 119+

Lim, Ivan S.; Laerdahl, Jon K.; Schwerdtfeger, Peter

doi:10.1063/1.1420747

Cited by 49 publications

(41 citation statements)

References 44 publications

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“…Their values, calculated from the Pople-Schofield Table I also provides polarizability data from analytical HartreeFock calculations published during the last 15 years (see the footnotes, data from earlier work may be found in the review literature cited above or in the references therein). Sometimes, but not always, the specially designed basis sets used in these studies work very well and lead to results very close to the numerical ones presented here, see e.g., [22,25,33].…”

Section: Nonrelativistic Resultssupporting

confidence: 58%

Static electric dipole polarizabilities for isoelectronic sequences

Koch

Andrae

2010

Int J of Quantum Chemistry

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Static electric dipole polarizabilities α d (Z, N) from numericalnonrelativistic restricted Hartree-Fock (RHF) finite-field calculations for closed-shell atoms and isoelectronic ions with N ≤ 120 electrons are presented. For those sequences where the electronic ground state of the neutral or nearly neutral members is conserved upon increase of the nuclear charge number Z, i.e., for the nine sequences with N = 2, 4, 10, 12, 18, 28, 30, 36, or 46 electrons, systems with total charge number Q = Z − N varying in the range −1 ≤ Q ≤ 90 were considered and their polarizability data fitted to rational functions of Q, with maximum absolute value of the relative error below 3%. The results presented here provide reference data (i) for algebraic approaches relying on basis functions and (ii) for the discussion of relativistic and correlation effects on polarizabilities along isoelectronic sequences.

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Section: Nonrelativistic Resultssupporting

confidence: 58%

Static electric dipole polarizabilities for isoelectronic sequences

Koch

Andrae

2010

Int J of Quantum Chemistry

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“…In another work, Lim et. al [72] have reported results for the alkali ions considering the scalar relativistic DK Hamiltonian and accounting for the spin-orbit coupling corrections through the MBPT(2) method using a fully relativistic four-component DF wave functions. In addition to the above mentioned systems we have also calculated α for Sc + and Y + ions, but there are no data available for comparison with our results.…”

Section: Resultsmentioning

confidence: 99%

Correlation trends in the ground-state static electric dipole polarizabilities of closed-shell atoms and ions

2013

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We employ the closed-shell perturbed relativistic coupled-cluster (RCC) theory developed by us earlier [Phys. Rev. A 77, 062516 (2008)] to evaluate the ground state static electric dipole polarizabilities (αs) of several atomic systems. In this work, we have incorporated a class of higher order many-body effects in our calculations that had not been taken into account in the above paper. We highlight their importance in improving the accuracies of αs. We also calculate the ground state αs of the inert gas atoms and several iso-electronic singly and doubly charged ions in order to make a comparative studies of the trends of the correlation effects. Furthermore, we have developed a method to construct intermediate diagrams that are required for the computations of the unperturbed singles and doubles coupled-cluster amplitudes. Our RCC results are compared with those of many-body perturbation theory at different orders to demonstrate the importance of higher order correlation effects for the accurate determination of (αs) of the systems that we have considered.

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“…In the parametrization of Reif and Hünenberger 65 (highlighted in color in Fig. 4), this additional constraint arises from using dispersion coefficients derived from experimental ionic polarizabilities 266 via the Slater-Kirkwood formula. 267 Interestingly, the r * and ε * parameters obtained here by fitting against the QM/MM RDFs are very close to those of Ref.…”

Section: J Optimization Of the Lennard-jones Interaction Parametersmentioning

confidence: 99%

Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

Hofer

Hünenberger

2018

The Journal of Chemical Physics

104

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The absolute intrinsic hydration free energy G • H + ,wat of the proton, the surface electric potential jump χ • wat upon entering bulk water, and the absolute redox potential V • H + ,wat of the reference hydrogen electrode are cornerstone quantities for formulating single-ion thermodynamics on absolute scales. They can be easily calculated from each other but remain fundamentally elusive, i.e., they cannot be determined experimentally without invoking some extra-thermodynamic assumption (ETA). The Born model provides a natural framework to formulate such an assumption (Born ETA), as it automatically factors out the contribution of crossing the water surface from the hydration free energy. However, this model describes the short-range solvation inaccurately and relies on the choice of arbitrary ion-size parameters. In the present study, both shortcomings are alleviated by performing first-principle calculations of the hydration free energies of the sodium (Na + ) and potassium (K + ) ions. The calculations rely on thermodynamic integration based on quantum-mechanical molecular-mechanical (QM/MM) molecular dynamics (MD) simulations involving the ion and 2000 water molecules. The ion and its first hydration shell are described using a correlated ab initio method, namely resolution-of-identity second-order Møller-Plesset perturbation (RIMP2). The next hydration shells are described using the extended simple point charge water model (SPC/E). The hydration free energy is first calculated at the MM level and subsequently increased by a quantization term accounting for the transformation to a QM/MM description. It is also corrected for finite-size, approximate-electrostatics, and potentialsummation errors, as well as standard-state definition. These computationally intensive simulations provide accurate first-principle estimates for G • H + ,wat , χ • wat , and V • H + ,wat , reported with statistical errors based on a confidence interval of 99%. The values obtained from the independent Na + and K + simulations are in excellent agreement. In particular, the difference between the two hydration free energies, which is not an elusive quantity, is 73.9 ± 5.4 kJ mol 1 (K + minus Na + ), to be compared with the experimental value of 71.7 ± 2.8 kJ mol 1 . The calculated values of G • H + ,wat , χ • wat , and V • H + ,wat ( 1096.7 ± 6.1 kJ mol 1 , 0.10 ± 0.10 V, and 4.32 ± 0.06 V, respectively, averaging over the two ions) are also in remarkable agreement with the values recommended by Reif and Hünenberger based on a thorough analysis of the experimental literature ( 1100 ± 5 kJ mol 1 , 0.13 ± 0.10 V, and 4.28 ± 0.13 V, respectively). The QM/MM MD simulations are also shown to provide an accurate description of the hydration structure, dynamics, and energetics. Published by AIP Publishing.

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Fully relativistic coupled-cluster static dipole polarizabilities of the positively charged alkali ions from Li+ to 119+

Cited by 49 publications

References 44 publications

Static electric dipole polarizabilities for isoelectronic sequences

Static electric dipole polarizabilities for isoelectronic sequences

Correlation trends in the ground-state static electric dipole polarizabilities of closed-shell atoms and ions

Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

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