Quantum indirect damping approximations

An Approximation for Quantum Indirect Damping [80] when Davydov Coupling Occurring... 

The different situations illustrated in Fig. 6 correspond more and more to approximate models when passing up to down. The top of the figure given the case described by Eq. (126) and corresponds to the reference quantum indirect damping. Below, is depicted the situation described by Eq. (146), where the Dyson time ordering operator is ignored in the quantum model. Further below is given the behavior that corresponds to both Eqs. (152) and (174), that is, to weak approximations on the classical limit of the quantum model [Eq. (152)] and to the semiclassical model [Eq. (174)]. At last, at the bottom we visualize the semiclassical model of Robertson and Yarwood [described by Eq. (185)]. 

Thus, owing to the suitability of quantum theory of indirect damping and to its difficulty in being generalized to complex situations, it appears to be of interest to find a suitable approximation to take into account simply the quantum indirect damping. This is the aim of this section [67]. 

This last expression may be viewed as the basic approximation in order to treat more easily the quantum indirect damping. 

Now, we show that the approximation that has been performed to treat the quantum indirect damping allows us to find other approximations for handling the quantum indirect relaxation in which the damping of the H-bond bridge is taken into account by aid of non-Hermitean effective Hamiltonians. 

Now, owing to the well-behaved character of the approached NHDH and CEL methods, it appears reasonable to apply them to more complex situations where, in the absence of Fermi resonance, the quantum indirect damping, and not only the direct damping [72], has to be treated beyond the adiabatic and harmonic approximations [71]. 

In Section IE, a theoretical approach of the quantum indirect damping of the H-bond bridge was exposed within the strong anharmonic coupling theory, with the aid of the adiabatic approximation. In Section III, this theory was shown to reduce to the Marechal and Witkowski and Rosch and Ratner quantum approaches. In Section IV, this quantum theory of indirect damping was shown to admit as an approximate semiclassical limit the approach of Robertson and Yarwood. 

Note that this last expression is nothing but the closed form [90] of the autocorrelation function obtained (as an infinite sum) in quantum representation III by Boulil et al.[87] in their initial quantum approach of indirect damping. Although the small approximation involved in the quantum representation III and avoided in the quantum representation II, both autocorrelation functions are of the same form and lead to the same spectral densities (as discussed later). 

Now, return to Fig. 14. The right and left bottom damped lineshapes (dealing respectively with quantum direct damping and semiclassical indirect relaxation) are looking similar. That shows that for some reasonable anharmonic coupling parameters and at room temperature, an increase in the damping produces approximately the same broadened features in the RY semiclassical model of indirect relaxation and in the RR quantum model of direct relaxation. Thus, one may ask if the RR quantum model of direct relaxation could lead to the same kind of prediction as the RY semiclassical model of indirect relaxation. 

Observe that all the mechanisms—that is, the classical indirect mechanism and the two quantum ones—predict a satisfactory isotope effect when the proton of the H bond is substituted by deuterium All the damping mechanisms induce approximately a l/y/2 low-frequency shift of the first moment and a 1 / y/2 narrowing of the breadth, which is roughly in agreement with experiment. As a consequence, the isotope effect does not allow us to distinguish between the two damping mechanisms. 

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