TY - JOUR
T1 - Effect of pressure on the Raman-active modes of zircon (ZrSiO4)
T2 - a first-principles study
AU - Sheremetyeva, Natalya
AU - Cherniak, Daniele J.
AU - Watson, E. Bruce
AU - Meunier, Vincent
N1 - Funding Information:
N.S. is supported by a Presidential Graduate Fellowship Award from the Rensselaer Polytechnic Institute. The authors acknowledge useful discussions with Liangbo Liang on calculation of Raman spectra from first-principles, who also provided scripts for evaluation of Raman intensities from dielectric tensors. Thoughtful comments from anonymous reviewers are gratefully acknowledged.
Publisher Copyright:
© 2017, Springer-Verlag GmbH Germany.
PY - 2018/2/1
Y1 - 2018/2/1
N2 - Density-functional theory (DFT) was employed in a first-principles study of the effects of pressure on the Raman-active modes of zircon (ZrSiO4), using both the generalized gradient and local density approximations (GGA and LDA, respectively). Beginning with the equilibrium structure at zero pressure, we conducted a calibration of the effect of pressure in a manner procedurally similar to an experimental calibration. For pressures between 0 and 7 GPa, we find excellent qualitative agreement of frequency–pressure slopes ∂ω/ ∂P calculated from GGA DFT with results of previous experimental studies. In addition, we were able to rationalize the ω vs. P behavior based on details of the vibrational modes and their atomic displacements. Most of the ∂ω/ ∂P slopes are positive as expected, but the symmetry of the zircon lattice also results in two negative slopes for modes that involve slight shearing and rigid rotation of SiO4 tetrahedra. Overall, LDA yields absolute values of the frequencies of the Raman-active modes in good agreement with experimental values, while GGA reproduces the shift in frequency with pressure especially well.
AB - Density-functional theory (DFT) was employed in a first-principles study of the effects of pressure on the Raman-active modes of zircon (ZrSiO4), using both the generalized gradient and local density approximations (GGA and LDA, respectively). Beginning with the equilibrium structure at zero pressure, we conducted a calibration of the effect of pressure in a manner procedurally similar to an experimental calibration. For pressures between 0 and 7 GPa, we find excellent qualitative agreement of frequency–pressure slopes ∂ω/ ∂P calculated from GGA DFT with results of previous experimental studies. In addition, we were able to rationalize the ω vs. P behavior based on details of the vibrational modes and their atomic displacements. Most of the ∂ω/ ∂P slopes are positive as expected, but the symmetry of the zircon lattice also results in two negative slopes for modes that involve slight shearing and rigid rotation of SiO4 tetrahedra. Overall, LDA yields absolute values of the frequencies of the Raman-active modes in good agreement with experimental values, while GGA reproduces the shift in frequency with pressure especially well.
UR - https://www.scopus.com/pages/publications/85021815842
UR - https://www.scopus.com/pages/publications/85021815842#tab=citedBy
U2 - 10.1007/s00269-017-0906-1
DO - 10.1007/s00269-017-0906-1
M3 - Article
AN - SCOPUS:85021815842
SN - 0342-1791
VL - 45
SP - 173
EP - 184
JO - Physics and Chemistry of Minerals
JF - Physics and Chemistry of Minerals
IS - 2
ER -