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Polarized micro‐Raman spectroscopy and ab initio phonon modes calculations of LuPO 4
Author(s) -
Sanson A.,
Giarola M.,
Bettinelli M.,
Speghini A.,
Mariotto G.
Publication year - 2013
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.4257
Subject(s) - raman spectroscopy , polarizability , ab initio , phonon , ab initio quantum chemistry methods , chemistry , molecular physics , density functional theory , normal mode , molecular vibration , atomic physics , computational chemistry , physics , condensed matter physics , optics , molecule , vibration , quantum mechanics , organic chemistry
The vibrational dynamics of lutetium orthophosphate (LuPO 4 ) single crystals was carefully investigated by means of polarized micro‐Raman spectroscopy and ab initio calculations. Eleven of the twelve independent components of the polarizability tensor, expected on the basis of the group theory for LuPO 4 , were selected in turn and assigned in symmetry. The only B 1g (2) Raman mode was not observed, likewise due to either its very small intensity or its nearness in energy with forbidden Raman modes, which spill and could hide it. Both Raman and infrared vibrational modes are evaluated by density‐functional theory calculations using effective core pseudo‐potential. The agreement between calculated and experimental frequencies is very good. On the basis of our ab initio results, and of reduced‐mass ratio considerations, the expected wavenumber of the missing B 1g (2) mode falls close to that of E g (3) mode peaked at about 306 cm −1 , and therefore we can definitively conclude that the observation of the missing B 1g (2) mode is masked by the spill‐over of this E g mode. Copyright © 2013 John Wiley & Sons, Ltd.