Covalent bond orders and atomic anisotropies from iterated stockholder atoms

Wheatley, Richard J.; Gopal, Angelica A.

doi:10.1039/c2cp23504h

Cited by 17 publications

(26 citation statements)

References 12 publications

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“…The overlap EBO values were taken directly from the literature. 61 All three methods give similar EBOs, but the NAOP results correlate most closely with the EBOs from simple molecular orbital theory. For these systems, the geometry and electron density were computed using the PW91 exchange-correlation functional with 6-311+G* basis sets.…”

Section: Effective Bond Orderssupporting

confidence: 73%

“…A recently reported correlation between EBOs and overlap populations for iterated stockholder atoms is an appealing strategy, because it can compute the EBOs directly from rr ð Þ without using the natural orbitals as input. 61 However, this strategy has yet to be tested on periodic materials. A more accurate and widely applicable method for computing EBOs could transform our understanding of periodic materials.…”

Section: Discussionmentioning

confidence: 99%

“…Tests also need to be performed to see whether explicit averaging over the hole, as shown in eqn (5.43), increases the EBO accuracy compared with the simplified correlation shown in eqn (5.40). Since eqn (5.40) was only tested for spin unpolarized systems, 61 additional tests need to be performed for spin polarized systems. For non-periodic systems, EBOs computed with proposed projectors should be carefully compared to NAOP bond orders.…”

Section: Effective Bond Ordersmentioning

confidence: 99%

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Computing Accurate Net Atomic Charges, Atomic Spin Moments, and Effective Bond Orders in Complex Materials

Manz

Sholl

2013

Computational Catalysis

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There are two types of methods for computing net atomic charges (NACs) and effective bond orders (EBOs). The first type computes these quantities using computationally efficient semi-empirical methods. Some noteworthy methods of this type for computing NACs include electronegativity and charge equalization methods, the split charge equilibration method, and charge-optimized many body (COMB) potentials. 1-6 EBOs can be estimated from semi-empirical bond distance to bond order correlations. 7-9 The second type computes NACs, atomic spin moments (ASMs), and EBOs from detailed quantum chemistry calculations such as density functional theory (DFT) or coupled-cluster theory. Some noteworthy methods of this type include: (a) the natural population RSC Catalysis Series No. 14 Computational Catalysis Edited by Aravind Asthagiri and Michael J. Janik

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Section: Effective Bond Orderssupporting

confidence: 73%

Section: Discussionmentioning

confidence: 99%

Section: Effective Bond Ordersmentioning

confidence: 99%

See 1 more Smart Citation

Computing Accurate Net Atomic Charges, Atomic Spin Moments, and Effective Bond Orders in Complex Materials

Manz

Sholl

2013

Computational Catalysis

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“…The NBO methods are used across the periodic table [296,297] and have been developed further [298,299]. Of other approaches, the Hirshfeld stockholder partitioning has been modified to produce bond orders [300]. In a brief summary, one can say that besides the basis-set dependence, the overlap populations calculated with nonspecialized quantum-chemical software may deviate substantially from the integral bond orders chemists expect for OS determination and are therefore not suitable for bond-order estimation.…”

Section: C-2 Calculations Of Bond Ordermentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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“…Therefore, it is interesting to know how far the anisotropic charge distribution can in fact be observed for the unperturbed halogen atom in a molecule. Very recently the anisotropy of several various atoms was estimated by means of integrations over stockholder atoms, and on that basis the anisotropy of halogen atoms was confirmed [35]. However, the estimated anisotropy of, e.g., Cl atom in HCl molecule was smaller than in the case of Si atom in SiH 4 molecule (30.2 9 10 -3 and 59.2 9 10 -3 , respectively).…”

Section: Introductionmentioning

confidence: 99%

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Bankiewicz

Palusiak

2012

Struct Chem

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A search through Crystal Structure Database was performed and the distances in contacts of XÁÁÁN,O, XÁÁÁH(N,O), and XÁÁÁC type were collected together with the information on spatial arrangement of the interacting fragments. A detailed statistical analysis showed that the shape of the halogen atom cannot be simply concluded on the basis of interatomic distances in crystal state although originally the concept of anisotropic charge distribution around halogen nuclei was postulated on the basis of such an analysis. It was proven that the conclusions in that case strongly depend on the type of center interacting with the halogen atom. Therefore, it was postulated that the shape of the halogen atom can be estimated for the unperturbed (due to intermolecular interactions) halogen atom. For this purpose, a method was provided to make possible a numerical quantification of the anisotropy of the halogen atom on the basis of electron density measurements performed within the framework of Atoms in Molecules Quantum Theory. The anisotropy of Cl and Br atoms in H 3 C-X and F 3 C-X (X=Cl, Br) was estimated for MP2 and DFT-B3LYP methods and several different basis sets. The influence of the method and the basis set on the degree of anisotropic distribution of electron density around halogen nuclei was discussed.Keywords Halogen bond Á The shape of the atom Á QTAIM Á DFT Á MP2 Á Basis set

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Covalent bond orders and atomic anisotropies from iterated stockholder atoms

Cited by 17 publications

References 12 publications

Computing Accurate Net Atomic Charges, Atomic Spin Moments, and Effective Bond Orders in Complex Materials

Computing Accurate Net Atomic Charges, Atomic Spin Moments, and Effective Bond Orders in Complex Materials

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

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