Photochemistry from first principles — advances and future prospects

Abstract

Detailed simulation of photochemistry poses considerable challenges because quantum mechanical effects are important in determining both the electronic potential energy surfaces and the subsequent nuclear dynamics. We provide a brief overview of the ab initio multiple spawning (AIMS) method which addresses the problem by solving both the electronic and nuclear Schrödinger equations simultaneously. We discuss our recent AIMS simulations of cis–trans photoisoimerization in ethylene as an example application. The prospects of the method for modeling of photochemistry in large organic molecules and condensed phases are assessed.