Penfold Thomas J, Worth Graham A
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
J Mol Graph Model. 2007 Oct;26(3):613-21. doi: 10.1016/j.jmgm.2007.01.012. Epub 2007 Feb 3.
It is extremely difficult to execute full quantum dynamics calculations on complex systems (more then three degrees of freedom) due to the exponential increase in computer resources required by these methods. Classical mechanics simulations do not suffer from this problem, but are unable to treat quantum mechanical phenomena such as non-adiabatic effects, which often play a vital role in photochemical processes. A method has been implemented for carrying out dynamical calculations using quasi-classical theory. The time dependent Schrödinger equation is solved using a swarm of trajectories treated under Newtonian laws and Tully's fewest switches trajectory surface hopping is applied to implement the surface switches. The method was applied to ozone, looking at the photodissociation that takes place after excitation into the Chappuis band of the absorption spectrum. While the goal is to treat larger systems, comparison can be made for ozone with numerically exact wavepacket calculations. The method proved successful at calculating quantities such as the rate of population transfer, but there were discrepancies in the details, especially when surface switching occurred from the lower state.
