Open AccessA new phase of solid iodine with different molecular covalent bonds
Author(s) -
Qifeng Zeng,
Zhi He,
Xiaojiao San,
Yanming Ma,
Fubo Tian,
Tian Cui,
Bingbing Liu,
Guangtian Zou,
Hokwang Mao
Publication year - 2008
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.0801280105
Subject(s) - molecular solid , intramolecular force , phase (matter) , dissociation (chemistry) , covalent bond , diatomic molecule , raman spectroscopy , chemistry , phase transition , chemical physics , molecular vibration , bromine , crystallography , molecule , thermodynamics , stereochemistry , organic chemistry , physics , optics
There is a great interest in the behavior of diatomic molecular solids under extremely high-pressure conditions that lead to pressure-induced metallization, molecular dissociation, and formation of atomic phase. The consensus has been that the phase-transition sequence that happened in both solid bromine and iodine is from a molecular phase (phase I), to an incommensurate phase (phase V), and then to an atomic phase (phase II), with increasing pressure. However, a puzzle remains unresolved for both solids: pressure-induced X and Y bands were observed in the Raman spectra in the molecular phase at low pressures, even before the onset of phase V. Here, we suggest a phase for solid iodine in such a low-pressure range (designated as phase I′) in which two different covalent intramolecular bonds coexist, based on first-principles calculations and later corroborated by x-ray diffraction experiments. The pressure dependence of the X and Y bands and other vibrational frequencies measured experimentally can be explained nicely by combining the vibrational modes of phase I and phase I′. These results help improve our understanding on the pressure-induced molecular dissociation and metallization in diatomic solids and may shed some light on the investigation of similar phenomena in solid H2 .