An atomic charge study of highly ionic diatomic molecular systems

Nakazato, Daniel T. I.; Sá, Eduardo L. de; Haiduke, Roberto Luiz Andrade

doi:10.1002/qua.22296

Cited by 9 publications

(10 citation statements)

References 19 publications

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“…Figure shows that Mulliken charges also compare well with the results of eq . Our results from eq are also in good agreement with literature − values [Table S3 (SI)] from other quantum chemistry approaches.…”

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confidence: 90%

Relationship between Dipole Moments and Harmonic Vibrational Frequencies in Diatomic Molecules

Hou

Bernath

2015

J. Phys. Chem. A

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Electric dipole moments and harmonic vibrational frequencies are two of the most important molecular properties in many fields of chemistry and physics. With the aid of classical physics, an empirical relationship between them was obtained for diatomic molecules as μd = kq(2)/(ReμAωe(2))(1/2), where k is a constant and μd, q, Re, μA, and ωe are the dipole moment, atomic charge, equilibrium bond length, reduced mass, and equilibrium vibrational frequency, respectively. This relation also provides the atomic charge q as a function of molecular dipole moment. Comparisons with over 60 molecules were made to test this relationship. For typical ionic molecules such as the alkali halides, the predicted dipole moments are in good agreement with the observed data assuming the atomic charges are 1 e. For general polar molecules, the estimated atomic charges obtained from the electric dipole moments are in good agreement with ab initio results for natural bond orbital and/or Mulliken populations.

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confidence: 90%

Relationship between Dipole Moments and Harmonic Vibrational Frequencies in Diatomic Molecules

Hou

Bernath

2015

J. Phys. Chem. A

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“…8 Some other studies of various chemical properties of BeO have also been reported; for example the valence band gap of BeO has been studied by Soulé de Bas et al, 9 the valence states of BeO have been study by Sorensen et al, 10 and the low-lying states of BeO have been studied by Irisawa et al 11 The partial atomic charges and dipole moment of LiF, KF, BeO, and MgO have been studied by Nakazato et al 12 In the present paper, we will study the BDE, IP, EA, EE, IE, and dipole moments for fourteen main-group diatomic molecules and one triatomic molecule (KOH).…”

Section: Introductionmentioning

confidence: 97%

Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms

Truhlar

2015

J. Chem. Theory Comput.

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Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive element, electron affinity of the electronegative bonding partner (EA), atomic excitation energy (EE) to prepare the valence states of the interacting partners, and interaction energy (IE) of the valence-prepared states. Adding Hartree-Fock exchange helps to obtain better results for atomic excitation energy, and this leads to improvements in getting the right answer for the right reason. The following functionals are singled out for reasonably good performance on all three of bond distance, BDE, and dipole moment: B97-1, B97-3, MPW1B95, M05, M06, M06-2X, M08-SO, N12-SX, O3LYP, TPSS, τ-HCTHhyb, and GAM; all but two (TPSS and GAM) of these functionals are hybrid functionals.

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“…In this context, several charge formalisms, based on arbitrary ways to divide the molecular electronic charge among the constituent atoms, have been analyzed for diverse purposes. [1][2][3][4][5][6][7][8][9][10][11] Recently, we carried out a study comparing the use of Mulliken, 12,13 Natural Population Analysis (NPA) 14,15 and Quantum Theory of Atoms In Molecules (QTAIM) [16][17][18] models in obtaining intramolecular charge uxes during bond stretchings in diatomic and linear triatomic molecules of diverse bond character. 19 It was shown that only charge uxes from QTAIM are consistent with simple physical arguments based on, for instance, dissociation of polar covalent bonds into neutral fragments and the existence of a harpoon mechanism in highly ionic diatomic molecules.…”

Section: Introductionmentioning

confidence: 99%

A theoretical analysis of atomic charge fluxes in chlorofluoromethanes and relationship with bonding character descriptors

Teodoro

Haiduke

2014

RSC Adv.

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An atomic charge study of highly ionic diatomic molecular systems

Cited by 9 publications

References 19 publications

Relationship between Dipole Moments and Harmonic Vibrational Frequencies in Diatomic Molecules

Relationship between Dipole Moments and Harmonic Vibrational Frequencies in Diatomic Molecules

Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms

A theoretical analysis of atomic charge fluxes in chlorofluoromethanes and relationship with bonding character descriptors

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