On Stress-Strain Responses and Young's Moduli of Single Alkane Molecules, A Molecular Mechanics Study Using the Modified Embedded-Atom Method

TL;DR

This study uses molecular mechanics with a modified embedded-atom method to simulate stress-strain responses of alkane molecules and polyethylene, proposing new methods for stress calculation and comparing results with theoretical and experimental data.

Contribution

Introduces three methods for calculating stress in alkane molecules and evaluates their accuracy against first-principles data, providing insights into Young's modulus predictions.

Findings

M1 method yields stress results close to theoretical data.

Predicted Young's modulus for PE chain aligns with ab initio calculations.

MEAM potential underestimates PE crystal Young's modulus.

Abstract

In this work, molecular mechanics simulations were performed using a modified embedded-atom method (MEAM) potential to generate the stress-strain responses of a series of n-alkane molecules from ethane (C$_2$H$_6$) to undecane (n-C$_{11}$H$_{24}$) in tensile deformation up to the point of bond rupture. The results are further generalized to a single polyethylene (PE) chain. Force, true Cauchy stress, true virial stress, and Young's moduli were calculated as a function of true strain for all of the molecules. In calculating the stress of a single molecule, three methods (designated in this work as M1, M2, and M3) are suggested based on three different metrics to quantify both the instantaneous molecular cross-sectional area and volume during deformation. The predictions of these methods are compared to theoretical, first-principles, and experimental data. M1 gives true Cauchy and true virial stress results that are essentially equivalent, suggesting that it is a better method for calculating stress in alkane molecules and, hence, PE single chain. The MEAM predictions of the average elastic modulus for a single PE chain using M1, M2, and M3 are 401 GPa, 172 GPa, and 147 GPa, respectively. Though these results are disparate, M1 gives a modulus value that is strikingly close to the ab initio-calculated value of 405 GPa for the -CH$_2$CH$_2$- repeat unit of PE at 0 K. To further test the MEAM potential, the Young's modulus (C$_{33}$ elastic constant) of an orthorhombic PE crystal cell was calculated, but its value (184 GPa) underestimates the DFT-calculated value of 316 GPa by 42%.