Temperature effects on the C–H symmetric stretching vibrational frequencies of guest hydrocarbon molecules in 512, 51262 and 51264 cages of sI and sII clathrate hydrates

Abstract

C–H symmetric stretching vibrational frequencies of CH₄, C₂H₄ and C₂H₆ molecules encapsulated in 5¹², 5¹²6² and 5¹²6⁴ cages of structures I (sI) and II (sII) clathrate hydrates measured by Raman spectroscopy in the temperature range of 93–183 K was analysed. The slopes of the symmetric stretch vibrational frequencies under changing temperatures (Δv/ΔT) for CH₄, C₂H₄ and C₂H₆ molecules encapsulated in sII 5¹²6⁴ cages were smaller than those for molecules in sI 5¹²6² cages, although sI 5¹²6² cages are smaller than sII 5¹²6⁴ cages. We compared the results of Δv/ΔT in this study with the geometrical properties of each host water cage, and these comparisons suggest that the geometry of host water cages affects Δv/ΔT.