Vibrational spectra of solid hydrogen sulfide: a lattice dynamics study

Abstract

A simple force constant model is described and applied to the vibrations of crystalline H2S and D2S in their low‐temperature ordered phase III, the structure of which has recently been determined. The model uses 14 adjustable parameters (three intramolecular and 11 intermolecular) to calculate the wavenumbers of 69 optical modes for each crystal, and good agreement with Raman and infrared data is obtained. The most important intermolecular interactions are confirmed to be hydrogen bonds, the formation of which results in a slight weakening of the molecular H — S bonds. In order to model the unusually wide range of lattice wavenumbers for these crystals, it is found necessary to introduce intermolecular bending force constants involving the hydrogen bonds. Copyright © 2000 John Wiley & Sons, Ltd.

Infrared Spectroscopy of Solid Hydrogen Sulfide and Deuterium Sulfide

“…For crystalline phase III, using the peak values in Tables and , the average lattice rotational vibrations are at 175 and 130 cm -1 (frequency ratio = 1.35) for H 2 S and D 2 S, respectively, while the lattice translational vibrations are at 88 and 86 cm -1 (frequency ratio = 1.02) for H 2 S and D 2 S, respectively. These values for crystalline phase III are in close agreement with previous studies. − , …”

“…5,6 This nonequivalence leads to splitting of some of the vibrations. 28,29 For these crystalline phase III spectra, the maximum peak positions for hydrogen sulfide are ν 2 at 1169, 1184, and 1189 cm -1 ; ν 1 at 2525 and 2536 cm -1 ; and ν 3 at 2548 cm -1 , while for deuterium sulfide they are ν 2 at 846, 856, and 860 cm -1 ; ν 1 at 1832 and 1840 cm -1 ; and ν 3 at 1852 cm -1 . These values give an average isotopic shift of 1.38.…”

“…Furthermore, the symmetric stretching (ν 1 ) and bending (ν 2 ) vibrations are split. This splitting is because the solid has eight molecules per unit cell, with two unique sulfur atoms but three unique S−H bonds. , This nonequivalence leads to splitting of some of the vibrations. , …”

Thermally-stable high energy storage performances and large electrocaloric effect over a broad temperature span in lead-free BCZT ceramic

“…It was observed that the intensity of the E(TO 2 ) mode decreased with increasing temperature, and an abrupt intensity change in this mode occurred at 355 K due to the structural change from ferroelectric (tetragonal) to paraelectric (cubic). 15,48…”

Vibrational spectra of arsenic triiodide: a lattice dynamics study

“…A complete listing, together with references, may be found in our most recent paper on hydrogen sulfide. 2 By reproducing the wavenumbers of observed Raman and infrared peaks of these crystals, while using as few adjustable parameters as possible, the model allows important information about their principal intra-and intermolecular forces to be obtained. In this work, we applied the technique to the interesting layered crystal AsI 3 .…”