title: First-principles investigation of the lattice vibrations in the alkali feldspar solid solution.
abstract: The heat capacities of Al, Si ordered alkali feldspars of different Na, K compositions were calculated using the density functional theory. The effect of the Na, K distribution, if random, ordered or clustered, on the resulting heat capacity was investigated on different cells with Ab50Or50composition. For all compositions and distributions studied, the excess heat capacity of mixing is positive at low temperatures with a maximum at ~60 K. This produces an increasing excess vibrational entropy that reaches a constant value above ~200 K. The amount of the excess heat capacity of Ab50Or50, however, depends on the Na, K distribution. Best agreement with measured excess heat capacities is achieved, if the distribution of Na and K is either ordered or clustered. The positive excess heat capacities can be attributed to a strong softening of the acoustic and the lowest optical modes related to a strong increase of Na-O bond lengths in samples with intermediate compositions. The softening of the lowest optical mode is, however, not reflected by thoroughly measured literature IR data. Comparing calculated and measured IR spectra suggests that the resolution of the measured spectra was insufficient for detecting the lowest IR-active modes.
authors.affiliation: Materialforschung und Physik, Universität Salzburg, Hellbrunnerstr. 34, 5020 Salzburg, Austria.
authors.forename: Artur
authors.initials: A
authors.lastname: Benisek
authors.affiliation: Materialforschung und Physik, Universität Salzburg, Hellbrunnerstr. 34, 5020 Salzburg, Austria.
authors.forename: Edgar
authors.initials: E
authors.lastname: Dachs
authors.affiliation: Materialforschung und Physik, Universität Salzburg, Hellbrunnerstr. 34, 5020 Salzburg, Austria.
authors.forename: Michael
authors.initials: M
authors.lastname: Grodzicki
keywords: CASTEP; DFT; Infrared spectra; KAlSi3O8; Low albite; Low microcline; NaAlSi3O8; Vibrational entropy