The ground-state potential energy surface (PES) of isomerization philosophy of ten normal-chain hexadiene isomers is computed by density functional methods using the geometries optimized at B3LYP/6-311++G (d, p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the uni-molecular isomerization reactions by transition state theory (TST) in the temperature range of 500-2500 K. Difference of rate constant between each hexadiene isomer is interpreted through the PES and 1:1 atom transfer, and only 2,4-hexadiene readily fulfills cis-cis to trans-trans conformation conversion. All the conversions are kinetically interpreted from the PES and ST geometry. (C) 2016 Elsevier B.V. All rights reserved.