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The anharmonicity of O-H stretching vibrations of water ice is characterized by use of a periodic implementation of the vibrational self-consistent field (VSCF) and vibrational configuration interaction (VCI) methods, which take phonon-phonon couplings explicitly into account through numerical evaluation of high-order terms of the nuclear potential. The low-temperature, proton-ordered phase of water ice (namely, ice XI) is investigated. The net effect of a coupled anharmonic treatment of stretching modes is not just a rigid blue-shift of the respective harmonic spectral frequencies but rather a complex change of their relative spectral positions, which cannot be captured by simple scaling strategies based on harmonic calculations. The adopted techniques allow for a hierarchical treatment of anharmonic terms of the nuclear potential, which is key to an effective identification of leading factors. We show that the anharmonic independent-mode approximation─only describing the "intrinsic anharmonicity" of the O-H stretches─is unable to capture the correct physics, and that couplings among O-H stretches must be described. Inspection of harmonic normal coordinates allows identification of specific features of the O-H stretching motions which most likely enable strong mode-mode couplings. Finally, by coupling O-H stretches to all other possible modes of ice XI (THz collective vibrations, molecular librations, bendings), we identify specific types of motion which significantly affect O-H stretching states: in particular, molecular librations are found to affect the stretching states more than molecular bendings.

Some Grenville-age rocks exposed in the uplifted region of the Hudson Highlands of southern New York are amphibole-dominant igneous rocks. The amphibole-rich rocks, which are locally pegmatitic in nature, are associated with magnetite ore and coarse-grained syenite; the ore was discovered and mined from the middle of the 18th century to the end of the 19th century. The amphiboles have attracted the attention of many researchers for nearly two centuries. Chemical analyses demonstrate that they are pargasite or hastingsite in composition and are particularly rich in Cl and K. High-precision crystal structure analyses of 11 Cl-rich amphiboles from the Hudson Highlands (0.0134