The structure of potassium chlorate at 77 and 298 K

Danielsen, Jacob; Hazell, Alan; Larsen, Finn

doi:10.1107/s0567740881004573

Cited by 20 publications

(20 citation statements)

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“…The calculated lattice constants, and volume with the standard DFT functionals and semiempirical dispersion correction scheme are summarized in Table I and the fractional co-ordinates are given in Table I of the supplementary material. 59 The obtained equilibrium lattice constants and volume using the PBE+G06 are in very good agreement with the experiment 20 and the corresponding CA-PZ and PBE values show large deviation from the experimental results at ambient pressure.…”

Section: A Structural Properties At Ambient Pressuresupporting

confidence: 74%

“…By taking experimental crystal structure as input, 20 we performed full structural optimization of the KClO 3 including lattice parameters and internal coordinates using standard LDA and GGA functionals. It is found that the calculated volume is underestimated by 12.6% within CA-PZ and overestimated by 7.5% within PBE functionals when compared to experimental volume and thus, the PBE volume is relatively closer to experiment than CA-PZ.…”

Section: A Structural Properties At Ambient Pressurementioning

confidence: 99%

“…23 So far, several Raman and IR measurements have been performed on KClO 3 at ambient as well as at extreme conditions. 20,[23][24][25][26][27][28][29][30] The Raman studies reveal that KClO 3 undergoes a pressure induced structural phase transition from ambient monoclinic (phase I) to rhombohedral (phase II) structure about 0.7 GPa, 27 or above 1 GPa. 31,32 Moreover, recent high pressure X-ray diffraction study (XRD) 33,34 shows that KClO 3 undergoes a rapid decomposition below 2 GPa, and it slows down above 2 GPa because of structural phase transformation from phase I to phase II.…”

Section: Introductionmentioning

confidence: 99%

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Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

Yedukondalu

Ghule

Vaitheeswaran

2013

The Journal of Chemical Physics

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High pressure behavior of potassium chlorate (KClO3) has been investigated from 0 to 10 GPa by means of first principles density functional theory calculations. The calculated ground state parameters, transition pressure, and phonon frequencies using semiempirical dispersion correction scheme are in excellent agreement with experiment. It is found that KClO3 undergoes a pressure induced first order phase transition with an associated volume collapse of 6.4% from monoclinic (P2(1)/m) → rhombohedral (R3m) structure at 2.26 GPa, which is in good accord with experimental observation. However, the transition pressure was found to underestimate (0.11 GPa) and overestimate (3.57 GPa) using local density approximation and generalized gradient approximation functionals, respectively. Mechanical stability of both the phases is explained from the calculated single crystal elastic constants. In addition, the zone center phonon frequencies have been calculated using density functional perturbation theory at ambient as well as at high pressure and the lattice modes are found to soften under pressure between 0.6 and 1.2 GPa. The present study reveals that the observed structural phase transition leads to changes in the decomposition mechanism of KClO3 which corroborates with the experimental results.

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Section: A Structural Properties At Ambient Pressuresupporting

confidence: 74%

Section: A Structural Properties At Ambient Pressurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

Yedukondalu

Ghule

Vaitheeswaran

2013

The Journal of Chemical Physics

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“…In Fig. 2 (16,17), and K2SO3 (34) compared with the orientations of the SO, PO, NH, and NC bonds in Me3SOI (this work), POBr3 (42,43), Me3NHI (58), Et3NHI (59), and Me4NI (1 1). The central atom of the trigonal-pyramidal grouping is S, Se, N, P, or C1; the axis is oriented vertically in the page.…”

Section: Spatial Extension Of the Lp In Crystalsmentioning

confidence: 99%

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

Knop¹,

Linden²,

Vincent³

et al. 1989

Can. J. Chem.

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The results of a detailed analysis of typical situations in crystals containing trigonal-pyramidal YEL3' species are used to argue that, per se, the lone electron pair (E, LP) on the Y atom determines neither the crystal structure nor the onentation of the Y EL3' units in the crystal. Considered as a space-filling entity, the LP has practically no effective volume of its own. Whatever space-filling or orienting properties may be associated with the presence of the LP, they are not autonomous; they arise from the intrinsic stereochemical involvement of the LP in the geometry of and the charge distribution in the free YEL3' ion or molecule and hence from the consequences of this geometry for crystal packing. Ab initio (6-31G*) calculations show that the electron density in the region of the LP in an ion is only slightly perturbed by the charge on the counter ion at distances observed in crystals. There is considerable similarity in the electron density distribution in the LP region of Y between free anionic (~0~~~ and free cationic (Me3S+) species. The problem of the so-called stereochemical inertness of the LP in the 14-electron octahedral Y E X~~-ions in crystals is examined in detail. It is concluded that the crystallographic Oh symmetry of the ion in cubic crystals is the result of dynamic averaging of possible orientations of the inherently noncubic YX62-octahedron (cf. the ab initio results for S e~l~~-) .Such averaging also appears to be responsible for the stereochemical "activation" or "inactivation" of the LP in thermally induced crystallographic transitions in the AYX3 halide perovskites and related crystals. To provide a firmer basis for the discussion of the LP, the crystal structures of the five title compounds have been determined. The crystal chemistry of these and related compounds is discussed.Key words: ab initio calculations, Me3S+ and SeC162-; group V trihalides; lone electron pair; trialkylsulfonium salts; VSEPR theory.OSVALD KNOP, ANTHONY LINDEN, BEVERLY R. VINCENT, S. C. CHOI, T. STANLEY CAMERON et RUSSELL J. BOYD. Can. J. Chem. 67, 1984Chem. 67, (1989.En se basant sur les rCsultats d'une analyse dCtaillte de situations typiques dans des cristaux contenant des espkces YEL3', on suggkre que la paire dYClectron libre (E, PL) sur l'atome Y ne dCtermine pas per se la structure cristalline ou I'orientation des unit& Y EL3' dans le cristal. ConsidCrte comme une entitC qui occupe du volume, la PL n'a pratiquement pas de volume effectif intrinskque. Quelles que soient les propriCtCs associCes avec la prCsence de la PL, elles ne sont pas autonomes; elles dCcoulent de l'implication stCrCochimique intrinskque de la PL dans la gComCtrie de et de la distribution de charge dans l'ion ou la molCcule YEL$ libre et ainsi des consCquences de cette gComCtrie sur I'empilement cristallin. Des calculs ab initio (6-3 lG*) dCmontrent que, aux distances observkes dans les cristaux, la densite tlectronique dans la rkgion de la PL d'un ion n'est que ICgkrement perturbCe par la charge du contre-ion. I1 existe une gr...

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“…Potassium chlorate forms a monoclinic crystal with two molecules per unit cell in the space group P2 1 /m [27]. The symmetry axis of the quadrupolar interaction is perpendicular to the plane defined by the three oxygens [28], which form a nearly tetrahedral arrangement with the chlorine atom.…”

Section: Methodsmentioning

confidence: 99%

Crossed-coil detection of two-photon excited nuclear quadrupole resonance

Eles

Michal

2005

Journal of Magnetic Resonance

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The structure of potassium chlorate at 77 and 298 K

Cited by 20 publications

References 3 publications

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

Crossed-coil detection of two-photon excited nuclear quadrupole resonance

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The structure of potassium chlorate at 77 and 298 K

Cited by 20 publications

References 3 publications

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

The lone electron pair and crystal packing: observations on pyramidal YEL3ε species, abinitio calculations, and the crystal structures of Me3SOI, Et3SI, (Me3S)2SnCl6, (Me3SO)2SnCl6, and (Et3S)2SnCl6

Crossed-coil detection of two-photon excited nuclear quadrupole resonance

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The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆