Polyatomic systems dynamics

In this chapter, we look at the techniques known as direct, or on-the-fly, molecular dynamics and their application to non-adiabatic processes in photochemistry. In contrast to standard techniques that require a predefined potential energy surface (PES) over which the nuclei move, the PES is provided here by explicit evaluation of the electronic wave function for the states of interest. This makes the method very general and powerful, particularly for the study of polyatomic systems where the calculation of a multidimensional potential function is an impossible task. For a recent review of standard non-adiabatic dynamics methods using analytical PES functions see [1]. 

The first study in which a full CASSCE treatment was used for the non-adiabatic dynamics of a polyatomic system was a study on a model of the retinal chromophore [86]. The cis-trans photoisomerization of retinal is the primary event in vision, but despite much study the mechanism for this process is still unclear. The minimal model for retinal is l-cis-CjH NHj, which had been studied in an earlier quantum chemisti7 study [230]. There, it had been established that a conical intersection exists between the Si and So states with the cis-trans defining torsion angle at approximately a = 80° (cis is at 0°). Two... 

New Methods in Quantum Molecular Dynamics of Large Polyatomic Systems... 

P. Jungwirth and R. B. Gerber. Quantum dynamics of large polyatomic systems using a classically based separable potential method. J. Chem. Phys., 102 6046-6056, 1995. 

Finally, application of the time-dependent density functional theory (TD-DFT) to the dynamics of the electrons and nucleus of a simple molecule has been realized recently. Although this method is only limited to quite small size of polyatomic systems at present, the approach is promising and has plenty rooms to be improved and extended. Thus, it may be wise to consider an effective combination of TD-DFT and the GME. 

A certain electronic transition in a polyatomic system can be equally described either within the adiabatic or within the diabatic basis set as the transitions can be induced either by the dynamic or by the static coupling,... 

R.B. Gerber and M.A. Ratner, Self-consistent field methods for vibrational excitations in polyatomic molecules, Adv. Chem. Phys., 70 (1988) 97. P. Jungwirth and R.B. Gerber, Quantum dynamics of large polyatomic systems using a classically based separable potential method, J. Chem. Phys., 102 (1995) 6046 Quantum dynamics of many atom systems by classically based separable potential (CSP) method Calculations for T (Ar),2 in full dimensionality, J. Chem. Phys., 102 (1995) 8855. 

REACTION DYNAMICS OF POLYATOMIC SYSTEMS FROM A AB + CD TO X + YCZj XY + CZj... 

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