For decades, downsizing has been a key issue for high performance and low cost of semiconductor, and extreme ultraviolet lithography is one of the promising candidates to achieve the goal. As a predominant process in extreme ultraviolet lithography on determining resolution and sensitivity, post exposure bake has been mainly studied by experimental groups, but development of its photoresist is at the breaking point because of the lack of unveiled mechanism during the process. Herein, we provide theoretical approach to investigate underlying mechanism on the post exposure bake process in chemically amplified resist, and it covers three important reactions during the process: acid generation by photo-acid generator dissociation, acid diffusion, and deprotection. Density functional theory calculation (quantum mechanical simulation) was conducted to quantitatively predict activation energy and probability of the chemical reactions, and they were applied to molecular dynamics simulation for constructing reliable computational model. Then, overall chemical reactions were simulated in the molecular dynamics unit cell, and final configuration of the photoresist was used to predict the line edge roughness. The presented multiscale model unifies the phenomena of both quantum and atomic scales during the post exposure bake process, and it will be helpful to understand critical factors affecting the performance of the resulting photoresist and design the next-generation material.