Gitterschwingungsspektren. IX. Pyritstruktur. FIR‐Spektren und Normalkoordinatenanalyse von MnS2, FeS2 und NiS2

Lutz, H. D.; Willich, P.

doi:10.1002/zaac.19744050207

Cited by 23 publications

(12 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The number and symmetries of the Raman and infrared-active modes of pyrite have been determined using group theoretical methods. 49 The irreducible representations of the vibrations of pyrite are:…”

Section: B Vibrational Contribution To the Energy Of Iron Disulfide mentioning

confidence: 99%

Density functional theory study of the relative stability of the iron disulfide polymorphs pyrite and marcasite

et al. 2010

View full text Add to dashboard Cite

The performance of density functional theory (DFT) has been widely examined with regard to its ability to predict the properties of minerals, though less attention has been given to the correct determination of the relative stability of structurally similar polymorphs. Here a detailed examination is performed of the numerical and theoretical factors that may influence the structure and relative energetics of two such polymorphs of iron disulfide, namely pyrite and marcasite, within density functional theory. Both the local density approximation and commonly used generalized gradient approximation exchange-correlation functionals, such as PBE, are found to predict that marcasite is more stable than pyrite, at variance with experiment. Allowing for the zero point energy of vibration fails to remedy this discrepancy. While inclusion of a 2 sufficiently large Hubbard U parameter for iron is found to reverse the stability, this comes at the expense of a very poor description of other properties. Examination of three generalized gradient approximations developed specifically for the solid-state, namely AM05, Wu-Cohen and PBEsol, demonstrates that all of these functionals offer a superior description of the structures and relative energies of pyrite and marcasite through correctly predicting that the former is the ground state phase at ambient conditions.

show abstract

Section: B Vibrational Contribution To the Energy Of Iron Disulfide mentioning

confidence: 99%

Density functional theory study of the relative stability of the iron disulfide polymorphs pyrite and marcasite

et al. 2010

View full text Add to dashboard Cite

show abstract

“…Thus, from far-infrared spectroscopic studies it was shown that the lattice dynamics of the isoelectronic OsS2 and PtP2 are very similar (Lutz et al 1976(Lutz et al , 1985 notwithstanding the different anionic units ($2 and P2) involved. In order to establish the Raman frequencies of pyrite-type compounds, especially with regard to the lattice dynamics of OsS2 and PtPz (the internal $2 and P2 stretching modes are only Raman allowed), we recorded single crystal Raman spectra of RuS2,RuSe2,OsS2,PtP2,and PtAs> Group theory treatment of the pyrite structure belonging to the space group Pa3-T 6 (Lutz and Willich 1974) yields five Raman-allowed zone centre phonon modes (unit cell (factor) group Th), viz., F=Ag+Eg+ 3Fg. The symmetry coordinates of the lattice vibrations are given elsewhere (Lutz and Willich 1974).…”

Section: Introductionmentioning

confidence: 99%

“…In order to establish the Raman frequencies of pyrite-type compounds, especially with regard to the lattice dynamics of OsS2 and PtPz (the internal $2 and P2 stretching modes are only Raman allowed), we recorded single crystal Raman spectra of RuS2,RuSe2,OsS2,PtP2,and PtAs> Group theory treatment of the pyrite structure belonging to the space group Pa3-T 6 (Lutz and Willich 1974) yields five Raman-allowed zone centre phonon modes (unit cell (factor) group Th), viz., F=Ag+Eg+ 3Fg. The symmetry coordinates of the lattice vibrations are given elsewhere (Lutz and Willich 1974). Until very recently, only incomplete Raman data of RuS2 and RuSe2 were available in the literature (Taguchi et al * This is contribution LXI of a series of papers on lattice vibration spectra 1987).…”

Section: Introductionmentioning

confidence: 99%

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Müller

Lutz

1991

Phys Chem Minerals

View full text Add to dashboard Cite

show abstract

“…Da ein entsprechendes Verhalten bei den IR-und Raman-Spektren, z. B. beim Vergleich von MnS2 und FeS2 , beobachtet wurde 3 ' 4 , beabsichtigten wir durch eine Kraftkonstantenrechnung zum Verständnis der Bindungseigenschaften von Pyriten beizutragen. Ferner sollten mit Hilfe einer numerischen Normalkoordinatenrechnung die von uns aufgrund geometrischer Über-legungen vorgeschlagenen Schwingungsformen des Pyritgitters 3 überprüft werden.…”

unclassified

“…Alle fünf optischen Phononen (k = 0) der Rasse Fu des Pyritgitters (Faktorgruppenanalyse [3][4][5][6] ) konnten bisher in den FIR-Spektren folgender Pyrite registriert werden 3 ' 7 : MnS2, FeS2 , RuS2 , RuSe2, RuTe2, OsS2 und PtP2 . Die fünf erlaubten Raman-aktiven Schwingungen wurden bisher noch bei keiner Verbindung vollständig beobachtet 4 ' 8 ' 9 .…”

unclassified

Gitterschwingungsspektren

Lutz

Willich

Haeuseler

1976

Zeitschrift Für Naturforschung A

Self Cite

View full text Add to dashboard Cite

Force constants and normal coordinates of MnS2 , FeS2 , RuS2, RuSe2, RuTe2, OsS2 and PtP2 are calculated based on the five ir active vibrations of the pyrite lattice. By setting up a valence force field consisting of short and long range M -X, X2 -X2 and M -M stretching constants it has proved possible to obtain good agreement between experimental and calculated frequencies with expection of FeS2 and RuS2 . The force constants corresponding to the shortest metal chalcogen distances (MnS2: 0.30, RuSe,: 0.88, RuTe2: 0.62, OsS2: 1.32, PtP2: 1.22 mdyn/A) are mainly responsible for the ir frequencies. For RuSe2 and RuTe, the forces between adjacent X2 groups are not negligible. Whereas the force constants of OsS2 and PtP2 are of comparable strength, the forces in MnS2 are significantly weaker than those in the other compounds. The normal coordinates of MnS2, OsS2 and PtP2 , and RuSe2 and RuTe2 show significant differences according to both the contribution of the 6 symmetry coordinates to the 5 ir active vibrations and the assignment of the spectra.

show abstract

Gitterschwingungsspektren. IX. Pyritstruktur. FIR‐Spektren und Normalkoordinatenanalyse von MnS₂, FeS₂ und NiS₂

Cited by 23 publications

References 6 publications

Density functional theory study of the relative stability of the iron disulfide polymorphs pyrite and marcasite

Density functional theory study of the relative stability of the iron disulfide polymorphs pyrite and marcasite

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Gitterschwingungsspektren

Contact Info

Product

Resources

About