Basis-set dependence of theoretical deformation density in NO<sub>2</sub>
                  <sup>−</sup>

Kikkawa, T.; Ohba, Shinya; Saito, Yoshihiko; Kamata, Shunichi; Iwata, Shuichi

doi:10.1107/s0108768187098264

Cited by 7 publications

(7 citation statements)

References 13 publications

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“…The Co--N coordination bond may be weakened by depopulation of the HOMO of the nitrite ion (see the scheme below). A driving force of the linkage isomerization seems to be the electrostatic attraction between the Co and O atoms, because the negative charge of NO2 is located almost totally on the O atoms (Kikkawa, Ohba, Saito, Kamata & Iwata, 1987;Okuda, Ohba, Saito, Ito & Shibuya, 1990).…”

Section: Nitro--* Nitrito Photoisomerizationmentioning

confidence: 99%

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Kubota¹,

Ohba²

1992

Acta Crystallogr B Struct Sci

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) which can be expressed by the model shown in Fig. 8. In this model the fl-phase containing only w3-and w4-phases gives the diffraction pattern for the fl-phase only. Thus, if the w2-phase in their model is replaced by the Wl-, w3-or w4-phase, the calculated diffraction patterns are similar to those calculated for the model shown in Fig. 4. The extra spots were observed for a specimen aged for 28 h (Fig. 9) in which the well developed w-phases are superimposed in the manner of the model. Fig. l0 shows the amplitudes of the characteristic and the extra diffraction spots for the model specimen and the arrows indicate the phase boundaries shown in Fig. 8. The intensities of the extra spots appear from the top surface of the w2-phase and the intensity of the 1/3 101 beam is weaker than that of the 2/3 101 beam. This tendency does not change with the position of the w~-fl-w2 sandwich at depths of ~ i 1 2 ~, ~ ana of the total thickness. This does not agree with the experimental result shown in Fig. 9 and it seems to be due to the difference in the number and modes of the sandwich realized in the specimen. There are also some intensity asymmetries in hkl and hkl in Fig. 10. SUKEDAI AND AKAO 627This may be due to differences in the superposition sequence of col-and w2-phases.The authors thanks are due to Mrs Y. Li for her help in taking the photograph (Fig. 9)

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Section: Nitro--* Nitrito Photoisomerizationmentioning

confidence: 99%

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Kubota¹,

Ohba²

1992

Acta Crystallogr B Struct Sci

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“…: !~i: '.~.Q~. ; HCO2-in (VIII), and theoretical deformation densities using the MIDI4* basis set for (c) CH3COz-(present work) and (d) HCOz- (Kikkawa et al, 1987). The contour interval in (a) and (b) is 0-1 e A -a, and that in (c) and ( Fig.…”

Section: Electron Density Distributionmentioning

confidence: 99%

“…A theoretical deformation density for the formate ion has been described previously (Kikkawa, Ohba, Saito, Kamata & Iwata, 1987). For the acetate ion, a similar calculation was carried out by an ab initio SCF method, using a MIDI4* basis set with the program system MOL YX (Nanbu, Nakata & Iwata, 1989) and on VAX 11/750 and NEWS-830 computers.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

Correlation of electron density and spin-exchange interaction in dimeric copper(II) formates, acetates and silanecarboxylates

Yamanaka¹,

Uekusa²,

Ohba³

et al. 1991

Acta Crystallogr B Struct Sci

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The structures of six dimeric copper(II) formates and acetates with picoline as an axial ligand, (I)-(VI), have been determined at room temperature and electron density distributions in lithium acetate dihydrate, (VII), and copper(II) formate diurea dihydrate, (VIII), have been studied at 120K. (VI) show no important geometrical differences in the Cu2(COO)4 cage between the copper acetates and formates. The observed deformation-density distributions in the CH3COO-(VII) and HCOO-(VIII) ions are in accord with theoretical expectations. Mulliken population analysis of eight carboxylate ions using STO-6G basis sets indicates that the electron population of the carboxylate group of the bridging ligand correlates with the -2J values of the binuclear copper(II) carboxylates. The key point that determines the strength of the spin-exchange interaction is the 2px orbital population of the carboxylate C atom (x is parallel to the C--R bond axis in the RCOO-ion). The electron population on a carboxylate O atom is shown to exhibit a roughly linear correlation with the pKa value of the parent carboxylic acid. The conundrum of why formate and fluoroacetate are exceptions to the correlation of -2J with pKa value has been solved in this paper.

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“…The electrostatic attraction between the Co and O atoms was proposed as driving force of the linkage isomerization due to the fact that the O atoms are rich in electrons than N in NO 2 ligand. 91,92 Fig. 8 shows the ELF Table 6 N/H-N and O/H-N NBO second-order perturbation energies E(2) (in kcal mol À1 ) and electron density (r) at the bcp and its Laplacian (V 2 r) in parenthesis computed at uB97XD/6-31+G isosurfaces of nitro and nitrito complexes and their cut planes.…”

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Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

2018

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Basis-set dependence of theoretical deformation density in NO₂ ⁻

Cited by 7 publications

References 13 publications

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Correlation of electron density and spin-exchange interaction in dimeric copper(II) formates, acetates and silanecarboxylates

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

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Basis-set dependence of theoretical deformation density in NO2 −

Cited by 7 publications

References 13 publications

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Nitro-nitrito linkage photoisomerization in crystals of pentaamminenitrocobalt(III) dichloride

Correlation of electron density and spin-exchange interaction in dimeric copper(II) formates, acetates and silanecarboxylates

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

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Basis-set dependence of theoretical deformation density in NO₂ ⁻