Correlation functions force

VER occurs as a result of fluctuating forces exerted by the bath on the system at the system s oscillation frequency O [5]. Fluctuating dynamical forces are characterized by a force-force correlation function. The Fourier transfonn of this force correlation function at Q, denoted n(n), characterizes the quantum mechanical frequency-dependent friction exerted on the system by the bath [5, 8]. 

Equation (C3.5.2 ) is a function of batli coordinates only. The VER rate constant is proportional to tire Fourier transfonn, at tire oscillator frequency Q, of tire batli force-correlation function. This Fourier transfonn is proportional as well to tire frequency-dependent friction q(n) mentioned previously. For example, tire rate constant for VER of tire Emdamental (v = 1) to tire ground (v = 0) state of an oscillator witli frequency D is [54]... 

Equation (C3.5.3) shows tire VER lifetime can be detennined if tire quantum mechanical force-correlation Emotion is computed. However, it is at present impossible to compute tliis Emotion accurately for complex systems. It is straightforward to compute tire classical force-correlation Emotion using classical molecular dynamics (MD) simulations. Witli tire classical force-correlation function, a quantum correction factor Q is needed 5,... 

VER in liquid O 2 is far too slow to be studied directly by nonequilibrium simulations. The force-correlation function, equation (C3.5.2), was computed from an equilibrium simulation of rigid O2. The VER rate constant given in equation (C3.5.3) is proportional to the Fourier transfonn of the force-correlation function at the Oj frequency. Fiowever, there are two significant practical difficulties. First, the Fourier transfonn, denoted [Pg.3041]

Figure C3.5.6. The computed Fourier transfonn at frequency co, of tire classical mechanical force-force correlation function for liquid O2 at 70 K from [M]- The VER rate is proportional to the value of ( " at tire O2...

From Eq. (70) we see that the time-dependent friction coefficient is given in terms of the force correlation function with projected dynamics. Instead, in MD simulations the time-dependent friction coefficient is computed using ordinary dynamics. 

From this expression we see that the friction cannot be determined from the infinite-time integral of the unprojected force correlation function but only from its plateau value if there is time scale separation between the force and momentum correlation functions decay times. The friction may also be estimated from the extrapolation of the long-time decay of the force autocorrelation function to t = 0, or from the decay rates of the momentum or force autocorrelation functions using the above formulas. 

In the canonical ensemble (P2) = 3kBTM and p M. In the microcanonical ensemble (P2) = 3kgT i = 3kBTMNm/(M + Nm) [49]. If the limit M —> oo is first taken in the calculation of the force autocorrelation function, then p = Nm and the projected and unprojected force correlations are the same in the thermodynamic limit. Since MD simulations are carried out at finite N, the study of the N (and M) dependence of (u(t) and the estimate of the friction coefficient from either the decay of the momentum or force correlation functions is of interest. Molecular dynamics simulations of the momentum and force autocorrelation functions as a function of N have been carried out [49, 50]. 

Fix the proton at some position s and run a MD simulation. The friction kernel is calculated from the force-force correlation function. 

The properties of the stochastic forces in the system of equations (3.31)-(3.35) are determined by the corresponding correlation functions which, usually (Chandrasekhar 1943), are found from the requirement that, at equilibrium, the set of equations must lead to well-known results. This condition leads to connection of the coefficients of friction with random-force correlation functions - the dissipation-fluctuation theorem. In the case under consideration, when matrixes f7 -7 and G 7 depend on the co-ordinates but not on the velocities of particles, the correlation functions of the stochastic forces in the system of equations (3.31) can be easily determined, according to the general rule (Diinweg 2003), as... 

The frozen-mode force correlation function CFF(t) not only closely resembles the vibrational friction [Equation (2)], it is often a rather accurate way of calculating it in practice (29,32). One reason for this fortunate circumstance is that in typical molecular vibrations the vibrational frequency is so large that the solvent hardly sees the effects of the dynamics on the forces (32). If we take this identification for granted, however,... 

The fluctuating forces F(t) on the rigid oscillator 2 are characterized by a time-dependent force-force correlation function (52,53),... 

Equation (4) provides a prescription for computing the VER rate, which can be used for diatomic and polyatomic molecules alike the force-force correlation function can be determined from a molecular simulation, and its Fourier transform at the desired frequency can be numerically... 

Some representative examples of common zero-temperature VER mechanisms are shown in Fig. 2b-f. Figures 2b,c describe the decay of the lone vibration of a diatomic molecule or the lowest energy vibrations in a polyatomic molecule, termed the doorway vibration (63), since it is the doorway from the intramolecular vibrational ladder to the phonon bath. In Fig. 2b, the excited doorway vibration 2 lies below large molecules or macromolecules. In the language of Equation (4), fluctuating forces of fundamental excitations of the bath at frequency 2 are exerted on the molecule, inducing a spontaneous transition to the vibrational ground state plus excitation of a phonon at Fourier transform of the force-force correlation function at frequency 2, denoted C( 2). 

Before preceding, it is useful to consider the form of the force-force correlation function, which is given in Equation (21), with Equations (22), (24), (25), (26) and (27). The form of the force-force correlation function, derived using density functional formalism, is employed because it permits the use of very accurate equations of state for solvents like ethane and CO2 to describe the density dependence and temperature dependence of the solvent properties. These equations of state hold near the critical point as well as away from it. Using the formalism presented above, we are able to build the known density and temperature-dependent properties of the... 

The force-force correlation function used here has a complicated form that can be determined by numerical evaluation. We examined the correlation function for ethane at 50° C as well as the critical density. With the Egelstaff quantum correction, the correlation function initially decays as 1-at2 for a very short time ( 15 fs). It then slows and becomes progressively slower at longer times. As mentioned above and as will be discussed in detail in connection with the experiments, the Fourier transform is taken at a relatively low frequency (150 cm-1), not the 2000 cm 1 oscillator frequency. For low frequencies, the very short time details of the correlation function are not of prime importance. Without the quantum correction, the strictly classical correlation function does not begin with zero slope at zero time, but, rather, it initially falls steeply. However, the quantum corrected function and the classical function have virtually identical shapes after 15 fs. As will be demonstrated below, the force-force correlation function contained in Equation (21) with Equations (22), (24), (25), (26), and (27) does a remarkable job of reproducing the density dependence observed experimentally. The treatment also works very well... 

The Ohmic model memory kernel admits an infinitely short memory limit y(t) = 2y5(t), which is obtained by taking the limit a>c —> oo in the memory kernel y(t) = yG)ce c [this amounts to the use of the dissipation model as defined by Eq. (23) for any value of ]. Note that the corresponding limit must also be taken in the Langevin force correlation function (29). In this limit, Eq. (22) reduces to the nonretarded Langevin equation ... 

Correspondingly, one can write a Kubo formula relating the generalized friction coefficient y(co) to the random force correlation function ... 

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