Nonadiabatic methods

B.C. Garrett, D.W. Schwenke, R.T. Skodje, D. Thirumalai, T.C. Thompson, D.G. Truhlar, Adiabatic and Nonadiabatic Methods for Energies, Lifetimes, and Branching Ratios of Reactive Resonances in Bimolecular Collisions, ACS Symposium Series 263, American Chemical Society, Washington DC, 1984,375. 

The modified nonadiabatic method described for the determination of the spontaneous combustion liability of subbituminous coals can yield satisfactory results. However, a more realistic measurement of a coal s self-heating tendency might be obtained through the use of an adiabatic system. In this case, heat derived from the coal oxidation would not be transferred to the surroundings. A spontaneous combustion instrument intended for field or lab/mine applications should be less complex, yet it should be capable of producing data that is reasonably accurate for predicting the self-heating characteristics of coals. 

The full dynamical treatment of electrons and nuclei together in a laboratory system of coordinates is computationally intensive and difficult. However, the availability of multiprocessor computers and detailed attention to the development of efficient software, such as ENDyne, which can be maintained and debugged continually when new features are added, make END a viable alternative among methods for the study of molecular processes. Eurthemiore, when the application of END is compared to the total effort of accurate determination of relevant potential energy surfaces and nonadiabatic coupling terms, faithful analytical fitting and interpolation of the common pointwise representation of surfaces and coupling terms, and the solution of the coupled dynamical equations in a suitable internal coordinates, the computational effort of END is competitive. 

In Chapter VI, Ohm and Deumens present their electron nuclear dynamics (END) time-dependent, nonadiabatic, theoretical, and computational approach to the study of molecular processes. This approach stresses the analysis of such processes in terms of dynamical, time-evolving states rather than stationary molecular states. Thus, rovibrational and scattering states are reduced to less prominent roles as is the case in most modem wavepacket treatments of molecular reaction dynamics. Unlike most theoretical methods, END also relegates electronic stationary states, potential energy surfaces, adiabatic and diabatic descriptions, and nonadiabatic coupling terms to the background in favor of a dynamic, time-evolving description of all electrons. 

Procedures enabling the calculation of bifurcation and limit points for systems of nonlinear equations have been discussed, for example, by Keller (13) Heinemann et al. (14-15) and Chan (16). In particular, in the work of Heineman et al., a version of Keller s pseudo-arclength continuation method was used to calculate the multiple steady-states of a model one-step, nonadiabatic, premixed laminar flame (Heinemann et al., (14)) a premixed, nonadiabatic, hydrogen-air system (Heinemann et al., (15)). 

For example, the ZN theory, which overcomes all the defects of the Landau-Zener-Stueckelberg theory, can be incorporated into various simulation methods in order to clarify the mechanisms of dynamics in realistic molecular systems. Since the nonadiabatic coupling is a vector and thus we can always determine the relevant one-dimensional (ID) direction of the transition in multidimensional space, the 1D ZN theory can be usefully utilized. Furthermore, the comprehension of reaction mechanisms can be deepened, since the formulas are given in simple analytical expressions. Since it is not feasible to treat realistic large systems fully quantum mechanically, it would be appropriate to incorporate the ZN theory into some kind of semiclassical methods. The promising semiclassical methods are (1) the initial value... 

It is getting more and more important to treat realistic large chemical and even biological systems theoretically by taking into account the quantum mechanical effects, such as nonadiabatic transition, tunneling, and intereference. The simplest method to treat nonadiabatic dynamics is the TSH method introduced... 

The method is composed of the following algorithms (1) transition position is detected along each classical trajectory, (2) direction of transition is determined there and the ID cut of the potential energy surfaces is made along that direction, (3) judgment is made whether the transition is LZ type or nonadiabatic tunneling type, and (4) the transition probability is calculated by the appropriate ZN formula. The transition position can be simply found by... 

In the above numerical examples the held parameter F is taken to be the laser frequency and the nonadiabatic transition used is the Landau-Zener type of curve-crossing. The periodic chirping method, however, can actually be more... 

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