On the forbidden graphene's ZO (out-of-plane optic) phononic band-analog vibrational modes in fullerenes

TL;DR

This study investigates how the vibrational density of states in fullerenes transitions to graphene behavior, revealing that pentagonal faces suppress certain out-of-plane phonon modes with thermodynamic implications.

Contribution

It demonstrates that pentagonal faces in fullerenes hinder the ZO phonon modes, compressing their frequency range and affecting thermodynamic properties, providing new insights into nanostructure vibrational behavior.

Findings

Fullerene VDOS converges to graphene's shape-line.

Pentagonal faces impede high-frequency ZO phonons.

ZO phonon band is compressed by 43%.

Abstract

The study of nanostructures' vibrational properties is at the core of nanoscience research, they are known to represent a fingerprint of the system as well as to hint the underlying nature of chemical bonds. In this work we focus on addressing how does the vibrational density of states (VDOS) of the carbon fullerene family ($C_n:~n=20\to720$ atoms) evolves from the molecular to the bulk material (graphene) behavior using density functional theory. We found that the fullerene's VDOS smoothly converges to the graphene characteristic shape-line with the only noticeable discrepancy in the frequency range of the out-of-plane optic (ZO) phonon band in graphene. From a comparison of both systems we obtain as main results that: 1)The pentagonal faces in the fullerenes impede the existence of the analog of the high frequency graphene's ZO phonons, 2)which in the context of phonons this could be interpreted as a compression (by 43\%) of the ZO phonon band by decreasing its maximum allowed radial-optic vibration frequency. 3)As a result, the deviation of fullerene's VDOS relative to graphene should result on important thermodynamical implications. The obtained insights can be extrapolated to other structures containing pentagonal rings such as nanostructure or as pentagonal defects in graphene.