Cerium (III) Complexes Modeling with Sparkle/PM3

Simas, Alfredo M.; Freire, Ricardo Oliveira; Rocha, Gerd B.

doi:10.1007/978-3-540-72586-2_44

Cited by 14 publications

(25 citation statements)

References 17 publications

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“…30 The geometric structures were optimized with density functional theory (DFT) using B3LYP exchangecorrelation hybrid functional. 31 The Pople's all electron basis set 6-311++G(3df, 3pd) 32 was used for H, Li, Na, K, Cl, and O, and the Stuttgart-Köln MCDHF RSC effective core potential (ECP, 28 core electrons) basis set aug-cc-pVTZ-PP 33 obtained from the EMSL basis set exchange 34 was used for I.…”

Section: B Theoretical Methodsmentioning

confidence: 99%

Photoelectron spectroscopy and theoretical study of M(IO3)2− (M = H, Li, Na, K): Structural evolution, optical isomers, and hyperhalogen behavior

Hou

Wen

et al. 2013

The Journal of Chemical Physics

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H(IO3)2(-) and M(IO3)2(-) (M = Li, Na, K) anions were successfully produced via electrospray ionization of their corresponding bulk salt solutions, and were characterized by combining negative ion photoelectron spectroscopy and quantum chemical calculations. The experimental vertical detachment energies (VDEs) of M(IO3)2(-) (M = H, Li, Na, K) are 6.25, 6.57, 6.60, and 6.51 eV, respectively, and they are much higher than that of IO3(-) (4.77 eV). The theoretical calculations show that each of these anions has two energetically degenerate optical isomers. It is found that the structure of H(IO3)2(-) can be written as IO3(-)(HIO3), in which the H atom is tightly bound to one of the IO3(-) groups and forms an iodic acid (HIO3) molecule; while the structures of M(IO3)2(-) can be written as (IO3(-))M(+)(IO3(-)), in which the alkali metal atoms interact with the two IO3(-) groups almost equally and bridge the two IO3(-) groups via two O atoms of each IO3(-) with the two MOOI planes nearly perpendicular to each other. In addition, the high VDEs of M(IO3)2(-) (M = Li, Na, K) can be explained by the hyperhalogen behavior of their neutral counterparts.

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Section: B Theoretical Methodsmentioning

confidence: 99%

Photoelectron spectroscopy and theoretical study of M(IO3)2− (M = H, Li, Na, K): Structural evolution, optical isomers, and hyperhalogen behavior

Hou

Wen

et al. 2013

The Journal of Chemical Physics

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“…As it can be seen from Table 1, the semiempirical calculations via Sparkle/AM1 and Sparkle/PM6 result in a notable error. Meanwhile, the Sparkle [17,18] model implementation in the oldest parameterization models by J. J. P. Stewart, namely PM3, [12] resulted in a very good agreement with the experiment (average deviation for two axes of 1.46%), with the deviation only insignificantly higher than that in DFT approach (deviation of 0.91%, Table 1, in italic).…”

Section: Computationsmentioning

confidence: 79%

“…The semiempirical computations were performed on the supercell using AM1, [11] , RM1, [3] PM3, [12] PM6, [13] and PM7 [2] semiempirical methods with the appropriate Sparkle models [5,[14][15][16][17][18][19] for lanthanide ions, Ln 31 were used for computations. They are the only methods supplied with the Sparkle model for Ce 31 and Tb 31 .…”

Section: Semiempirical Computationsmentioning

confidence: 99%

“…This compound is known to be a photostable and efficient luminophore of potential applications in various fields. Semiempirical methods AM1, [11] RM1, [3] PM3, [12] PM6, [13] and PM7 [2] with Sparkle model [5,[14][15][16][17][18][19] for Ln 31 were used. Conversely, it is chemically and structurally simple and easy to model.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, we have modelled the impact of the dopant amount (the x value) on the cell parameters of Ce 1-x Tb x F 3 . Semiempirical methods AM1, [11] RM1, [3] PM3, [12] PM6, [13] and PM7 [2] with Sparkle model [5,[14][15][16][17][18][19] for Ln 31 were used. The ab initio Generalized Gradient Approximation with Hubbard U, GGA1U [20] Projector Augmented Wave (PAW) DFT [21,22] method was used for comparison.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Semiempirical and DFT computations of the influence of Tb(III) dopant on unit cell dimensions of cerium(III) fluoride

et al. 2014

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Several computational methods, both semiempirical and ab initio, were used to study the influence of the amount of dopant on crystal cell dimensions of CeF3 doped with Tb(3+) ions (CeF3 :Tb(3+) ). AM1, RM1, PM3, PM6, and PM7 semiempirical parameterization models were used, while the Sparkle model was used to represent the lanthanide cations in all cases. Ab initio calculations were performed by means of GGA+U/PBE projector augmented wave density functional theory. The computational results agree well with the experimental data. According to both computation and experiment, the crystal cell parameters undergo a linear decrease with increasing amount of the dopant. The computations performed using Sparkle/PM3 and DFT methods resulted in the best agreement with the experiment with the average deviation of about 1% in both cases. Typical Sparkle/PM3 computation on a 2×2×2 supercell of CeF3:Tb3+ lasted about two orders of magnitude shorter than the DFT computation concerning a unit cell of this material.

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The lanthanide contraction within the sparkle model

Freire

Simas²

2010

Int J of Quantum Chemistry

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The sparkle model has been introduced to allow the a priori quantum chemical calculation of properties, mainly geometries, of lanthanide complexes. In this work, we compute Sparkle/PM3 optimized geometries for the isostructural series of complexes Ln[TREN-1,2-HOIQO(H 2 O) 2 ] and Ln[(H2O) 9 ] 3þ , with Ln ¼ La-Lu (except Pm). The results reveal the expected contraction for each series of complexes. We conclude that the lanthanide contraction phenomenon is indeed present within Sparkle/ PM3, a fact which can only reinforce the sparkle model as a powerful tool for the prediction and rationalization of the geometric features of lanthanide complexes and for their a priori design.

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Cerium (III) Complexes Modeling with Sparkle/PM3

Cited by 14 publications

References 17 publications

Photoelectron spectroscopy and theoretical study of M(IO3)2− (M = H, Li, Na, K): Structural evolution, optical isomers, and hyperhalogen behavior

Photoelectron spectroscopy and theoretical study of M(IO3)2− (M = H, Li, Na, K): Structural evolution, optical isomers, and hyperhalogen behavior

Semiempirical and DFT computations of the influence of Tb(III) dopant on unit cell dimensions of cerium(III) fluoride

The lanthanide contraction within the sparkle model

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