An Introduction to the Quantum Theory of Atoms in Molecules

Matta, Chérif F.; Boyd, Russell J.

doi:10.1002/9783527610709.ch1

Cited by 478 publications

(654 citation statements)

References 112 publications

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“…The bonding within the individual equilibrium structures was also analyzed by locating the bond critical points (BCP) using atoms-in-molecules (AIM) theory [31][32], which is based on a topological analysis of the electronic density at the BCPs, and is a good descriptor of the bond strength or weakness.…”

Section: Computationalmentioning

confidence: 99%

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

Salpin

Guillaumont

Tortajada

et al. 2009

J. Am. Soc. Mass Spectrom.

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The gas-phase interactions between lead(II) ions and 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil have been investigated by combining mass spectrometry and theoretical calculations. The most abundant complexes observed, namely [Pb(thiouracil) Ϫ H] ϩ , have been studied by MS/MS experiments. Cationization by the metal allows an unambiguous characterization of the sulfur position, several fragment ions being specific of each isomer. Moreover, compared with the uracil fragmentation, new fragmentation channels are observed: elimination of PbS or total reduction of the metal. Calculations performed on the different structures, including tautomers, show that sulfur is the preferred complexation site, suggesting the greater affinity of lead for sulfur. The most stable structures are always preferentially bidentate. Natural population analysis indicates a charge transfer from the base to the metal with a more pronounced covalent character for sulfur compared to oxygen. Energetic profiles associated with the main fragmentations have been described. (J Am Soc Mass Spectrom 2009, 20, 359 -369)

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Section: Computationalmentioning

confidence: 99%

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

Salpin

Guillaumont

Tortajada

et al. 2009

J. Am. Soc. Mass Spectrom.

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“…The relationship between charge density topology and elements of molecular structure and bonding was noted by Bader 35 . This relationship, Bader's quantum theory of atoms in molecules (QTAIM) [35][36][37] , is now a well-recognized tool for analyzing electron density, describing interatomic interactions, and rationalizing chemical bonding. Table 1, in which the statistic fitting parameters (R wp and GOF) indicate the quality of structural refinement data is acceptable.…”

Section: Introductionmentioning

confidence: 99%

An Experimental and Computational Study of β-AgVO₃: Optical Properties and Formation of Ag Nanoparticles

et al. 2016

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“…[8,19] In this context, it is interesting to note that at the same nonrelativistic level, a bond-critical point is located between the two Te atoms in N1 a in an atoms-in-molecules analysis. [20] The variation in the computed J values can be rationalized through the extent of overlap between the densities of the Te lone pairs ( Figure S5). Compared to typical "through-space" n J( 31 P, 31 P) couplings, the Te,Te couplings of this study are larger by at least one order of magnitude.…”

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confidence: 95%

Weak Te,Te Interactions through the Looking Glass of NMR Spin–Spin Coupling

et al. 2013

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Most of the tools for quantifying the extent of chemical bonding between two atoms are quantum-chemical in nature. None of them are unambiguous, however, and different analyses can lead to conflicting interpretations, even concerning the most fundamental question of whether or not atoms are linked by a chemical bond. [1,2] One of the indicators that can be probed experimentally is the indirect spin-spin coupling constant (SSCC). For instance, observation of spinspin coupling across hydrogen bonds [3] has been taken as evidence for covalent contributions to this kind of bonding. For atoms within the same molecule that are close in space, but not linked through a direct formal bond, the question arises, how much of the observed coupling is transmitted through a succession of bonds that eventually links them ("through-bond coupling"), and how much is due to interaction through the overlap of lone pairs ("through-space coupling"). Again, a variety of quantum-chemical tools have been developed to address this question.A rigid scaffold that is used to achieve such spatial proximity is the naphthalene framework, in which substituents in the peri (1,8) positions have a typical separation of around 3 . [4] Through-space J( 19 F, 19 F) SSCCs, long known for their distance dependence, [5a] have been studied in some detail in peri-difluoronaphthalenes. [5b,c] Similarly, J( 31 P, 31 P) values in peri-bis(phosphino)naphthalenes have been attributed to through-space coupling, [6] and J( 77 Se, 77 Se) values in peri-bis(seleno) derivatives have been analyzed in detail through quantum-chemical computations. [7] In systematic studies of naphthalene (N) and acenaphthene (A) derivatives with pnictogen and chalcogen atoms in the peri positions, it became apparent that for the heavier congeners, steric repulsion is partly counterbalanced by attractive interactions. In particular with Te substituents, formally nonbonded, "across-the-bay" distances are significantly shorter than the sum of the van-der-Waals radii, which has been traced back to weak donor-acceptor interactions and the onset of 3-center-4-electron (3c4e) bonding. [8] For instance in N1 and A1 (Scheme 1), Te···Te distances of around 3.3 are observed in the solid state (ca. 0.7 below the sum of the vdW radii), and Wiberg bond indices [9] (WBIs, a measure for the covalent character of a bond, approaching WBI = 1 for a true single bond) of around 0.15 have been computed. Slightly larger WBIs of approximately 0.18 have been obtained for cationic methylated species N2 and A2, despite a slightly longer Te-Te separation (ca. 3.4 ). [10] These unsymmetrical systems show remarkably large J( 125 Te, 125 Te) SSCCs, formally 4 J values, of 1093.0 Hz and 945.8 Hz in N2 and A2, respectively. [10] We now report even larger couplings in N1 and A1, along with computational conformational analysis underlining the potential of this property as a structural and interpretative method.The computed (ZORA-SO/BP//B3LYP level) [11] J( 125 Te, 125 Te) SSCCs in N2 and A2 (1490 and 1377 Hz, respec...

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An Introduction to the Quantum Theory of Atoms in Molecules

Cited by 478 publications

References 112 publications

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

An Experimental and Computational Study of β-AgVO₃: Optical Properties and Formation of Ag Nanoparticles

Weak Te,Te Interactions through the Looking Glass of NMR Spin–Spin Coupling

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An Introduction to the Quantum Theory of Atoms in Molecules

Cited by 478 publications

References 112 publications

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

Gas-phase interactions between lead(II) ions and thiouracil nucleobases: A combined experimental and theoretical study

An Experimental and Computational Study of β-AgVO3: Optical Properties and Formation of Ag Nanoparticles

Weak Te,Te Interactions through the Looking Glass of NMR Spin–Spin Coupling

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An Experimental and Computational Study of β-AgVO₃: Optical Properties and Formation of Ag Nanoparticles