Golden rules

Femii s Golden Rule expresses the rate of transitions between b and a as... 

Note that if we identify the sum over 8-fimctions with the density of states, then equation (A1.6.88) is just Femii s Golden Rule, which we employed in section A 1.6.1. This is consistent with the interpretation of the absorption spectmm as the transition rate from state to state n. 

It should be noted that in the cases where y"j[,q ) > 0, the centroid variable becomes irrelevant to the quantum activated dynamics as defined by (A3.8.Id) and the instanton approach [37] to evaluate based on the steepest descent approximation to the path integral becomes the approach one may take. Alternatively, one may seek a more generalized saddle point coordinate about which to evaluate A3.8.14. This approach has also been used to provide a unified solution for the thennal rate constant in systems influenced by non-adiabatic effects, i.e. to bridge the adiabatic and non-adiabatic (Golden Rule) limits of such reactions. 

Many experimental techniques now provide details of dynamical events on short timescales. Time-dependent theory, such as END, offer the capabilities to obtain information about the details of the transition from initial-to-final states in reactive processes. The assumptions of time-dependent perturbation theory coupled with Fermi s Golden Rule, namely, that there are well-defined (unperturbed) initial and final states and that these are occupied for times, which are long compared to the transition time, no longer necessarily apply. Therefore, truly dynamical methods become very appealing and the results from such theoretical methods can be shown as movies or time lapse photography. 

The simplest theoretical description of the photon capture cross-section is given by Fermi s Golden Rule... 

First-Order Fermi-Wentzel "Golden Rule"... 

This expresses the widely used El approximation to the Fermi-Wentzel golden rule. 

The first-order El "golden-rule" expression for the rates of photon-induced transitions can be recast into a form in which certain specific physical models are easily introduced and insights are easily gained. Moreover, by using so-called equilibrium averaged time correlation functions, it is possible to obtain rate expressions appropriate to a... 

So, the final result is the order golden rule expression ... 

A simple method for predicting electronic state crossing transitions is Fermi s golden rule. It is based on the electromagnetic interaction between states and is derived from perturbation theory. Fermi s golden rule states that the reaction rate can be computed from the first-order transition matrix and the density of states at the transition frequency p as follows ... 

The golden rule is a reasonable prediction of state-crossing transition rates when those rates are slow. Crossings with fast rates are predicted poorly due to the breakdown of the perturbation theory assumption of a small interaction. 

The first type of interaction, associated with the overlap of wavefunctions localized at different centers in the initial and final states, determines the electron-transfer rate constant. The other two are crucial for vibronic relaxation of excited electronic states. The rate constant in the first order of the perturbation theory in the unaccounted interaction is described by the statistically averaged Fermi golden-rule formula... 

Comparison of (1.14), (2.47a) and (2.60a) reveals the universality of the golden rule in the description of both the nonadiabatic and adiabatic chemical reactions. However, the matrix elements entering into the golden-rule formula have quite a different nature. In the case of an adiabatic reaction it comes from tunneling along the reaction coordinate, while for a nonadiabatic... 

In the time-dependent perturbation theory [Landau and Lifshitz 1981] the transition probability from the state 1 to 2 is related with the perturbation by the golden rule,... 

Moreover, eq. (5.64) is nothing but the omnipresent golden rule. To see this just notice that the density of final states is identically equal to... 

Substitution of this for the golden-rule expression (1.14) together with the renormalized tunneling matrix element from (5.60) gives (5.64), after thermally averaging over the initial energies E-,. In the biased case the expression for the forward rate constant is... 

When Va is small so that the transition is nonadiabatic, the usual golden-rule analysis based on (5.66) can be performed to give [Garg et al. 1985 Wolynes 1987]... 

The golden rule, therefore, is to deal only with consultants, contractors, plant suppliers and water-conditioning experts whose experience and standing are known to be good. If there is any doubt, references should be sought and followed up. Water and effluent installations are a relatively minor cost item in any plant, but their failure can be disastrous. It is foolish to make false economies on so essential a service. 

From Wentzel-Fermi Golden Rule to the Time Domain... 

The expression for the rate R (sec ) of photon absorption due to coupling V beriveen a molecule s electronic and nuclear charges and an electromagnetic field is given through first order in perturbation theory by the well known Wentzel Fermi golden rule formula (7,8) ... 

Let us now consider how similar the expression for rates of radiationless transitions induced by non Bom-Oppenheimer couplings can be made to the expressions given above for photon absorption rates. We begin with the corresponding (6,4g) Wentzel-Fermi golden rule expression given in Eq. (10) for the transition rate between electronic states Ti,f and corresponding vibration-rotation states Xi,f appropriate to the non BO case ... 

An accurate calculation of the heat conductivity requires solving a kinetic equation for the phonons coupled with the multilevel systems, which would account for thermal saturation effects and so on. We encountered one example of such saturation in the expression (21) for the scattering strength by a two-level system, where the factor of tanh((3co/2) reflected the difference between thermal populations of the two states. Neglecting these effects should lead to an error on the order of unity for the thermal frequencies. Within this single relaxation time approximation for each phonon frequency, the Fermi golden rule yields, for the scattering rate of a phonon with Ha kgT,... 

In order to compute the lifetime of a phonon of energy E, one averages the Golden Rule scattering rate (7ig A /pCj )tanh(p /2) with respect to n(e, A), subject to the resonance condition E = y/EA + A [8, 11, 93]. This yields two contributions to the decay rate ... 

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