Non-adiabatic system

APPLYING DIRECT MOLECULAR DYNAMICS TO NON-ADIABATIC SYSTEMS... 

Information about critical points on the PES is useful in building up a picture of what is important in a particular reaction. In some cases, usually themially activated processes, it may even be enough to describe the mechanism behind a reaction. However, for many real systems dynamical effects will be important, and the MEP may be misleading. This is particularly true in non-adiabatic systems, where quantum mechanical effects play a large role. For example, the spread of energies in an excited wavepacket may mean that the system finds an intersection away from the minimum energy point, and crosses there. It is for this reason that molecular dynamics is also required for a full characterization of the system of interest. 

A further model Hamiltonian that is tailored for the treatment of non-adiabatic systems is the vibronic coupling (VC) model of Koppel et al. [65]. This provides an analytic expression for PES coupled by non-adiabatic effects, which can be fitted to ab initio calculations using only a few data points. As a result, it is a useful tool in the description of photochemical systems. It is also very useful in the development of dynamics methods, as it provides realistic global surfaces that can be used both for exact quantum wavepacket dynamics and more approximate methods. 

One way to overcome this problem is to start by setting up the ensemble of trajectories (or wavepacket) at the transition state. If these bajectories are then run back in time into the reactants region, they can be used to set up the distribution of initial conditions that reach the barrier. These can then be run forward to completion, that is, into the products, and by using transition state theory a reaction rate obtained [145]. These ideas have also been recently extended to non-adiabatic systems [146]. 

As shown above in Section UFA, the use of wavepacket dynamics to study non-adiabatic systems is a trivial extension of the methods described for adiabatic systems in Section H E. The equations of motion have the same form, but now there is a wavepacket for each electronic state. The motions of these packets are then coupled by the non-adiabatic terms in the Hamiltonian operator matrix elements. In contrast, the methods in Section II that use trajectories in phase space to represent the time evolution of the nuclear wave function cannot be... 

If more than one electronic state is involved, then the electronic wave function is free to contain components from all states. For example, for non-adiabatic systems the elecbonic wave function can be expanded in the adiabatic basis set at the nuclear geometry R t)... 

To use direct dynamics for the study of non-adiabatic systems it is necessary to be able to efficiently and accurately calculate electronic wave functions for excited states. In recent years, density functional theory (DFT) has been gaining ground over traditional Hartree-Fock based SCF calculations for the treatment of the ground state of large molecules. Recent advances mean that so-called time-dependent DFT methods are now also being applied to excited states. Even so, at present, the best general methods for the treatment of the photochemistry of polyatomic organic molecules are MCSCF methods, of which the CASSCF method is particularly powerful. 

Quantum chemical methods, exemplified by CASSCF and other MCSCF methods, have now evolved to an extent where it is possible to routinely treat accurately the excited electronic states of molecules containing a number of atoms. Mixed nuclear dynamics, such as swarm of trajectory based surface hopping or Ehrenfest dynamics, or the Gaussian wavepacket based multiple spawning method, use an approximate representation of the nuclear wavepacket based on classical trajectories. They are thus able to use the infoiination from quantum chemistry calculations required for the propagation of the nuclei in the form of forces. These methods seem able to reproduce, at least qualitatively, the dynamics of non-adiabatic systems. Test calculations have now been run using duect dynamics, and these show that even a small number of trajectories is able to produce useful mechanistic infomiation about the photochemistry of a system. In some cases it is even possible to extract some quantitative information. 

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