Extended versus localized vibrations: the case of L-cysteine and L-cystine amino acids

Abstract

A detailed quantitative analysis of the specific heat in the $1.8-300$ K temperature range for L-cysteine and L-cystine amino acids was presented. We observed not extended but a sharp transition at $\sim 76$ K for L-cysteine. This transition was associated to the thiol group ordering and the order-disorder transition was adequately modeled by a 2D Ising model. The energy difference among two thiol configurations was found to be $-J=\varepsilon_{A}-\varepsilon_{B}=-66.6$ cal/mole. Besides, we conducted a study of phonon and rotor contributions to the specific heat and we proposed a generalization of Debye model. It was possible to evaluate the exponent of the $g(\omega)$, leading to the result that it corresponds to the Debye model for L-cysteine, which implies that the boson peak in this system is due to a maximum in the $C_{coup}(\omega)$ and also that the plane wave of wave-vector $\vec{q}$ is a good approximation to describe the phonons. On the other hand the origin of the boson peak for L-cystine correlates to a peak in $g(\omega)$ and phonons in L-cystine could be well represented by strongly attenuated plane waves or localized vibrations. Lastly, the analysis at very low temperature ($T<3$ K) indicated that L-cysteine presented a nearly temperature independent behaviour which is opposite to which is widely observed in systems with glassy characteristics within the Two-Level System (TLS) framework.