Bath interaction theory

To obtain the oscillator-bath interaction term, we argue that the solute s instantaneous size depends linearly on the breathing coordinate q multiplied by a dimensionless coefficient a. The latter is treated as the single adjustable parameter in the theory, which should on physical grounds be less than but on the order of unity. This leads to (2)... 

Momentum representation of the solute/bath interaction in the dynamic theory of chemical processes in condensed phase Bosanac S.D. 

It is important to note that the model of Fig. 18.1 cannot account for thermal interactions between the molecule and its environment. As discussed above, it contains elements of relaxation, and if the continuum / represents excited states ofthe environment the transition s / describes relaxation by energy transfer from the molecule to environmental motions. However, the opposite process of heating the molecule by energy transfer from a hot environment cannot be described in this way. The R and L continua can represent only zero-temperature radiative and nonradiative baths. The theory is therefore applicable to zero temperature situations only. 

A possibility to overcome this limitation of the above conical-intersection models, at least in a quahtative manner, is to consider anhar-monic couplings of the active degrees of freedom of the conical intersection with a large manifold of spectroscopically inactive vibrational modes. The effect of such a couphng with an environment has been investigated for the pyrazine model in the weak-coupling limit (Redfield theory) in Ref. 19. The simplest ansatz for the system-bath interaction, which is widely employed in quantum relaxation theory assumes a coupling term which is bilinear in the system and bath operators... 

Despite the fact that the exact j or TZ can be formally expressed in terms of an infinite series expansion, its evaluation, however, amounts to solve the total composite system of infinite degrees of freedom. In practice, one often has to exploit weak system-bath interaction approximations and the resulting COP [Eq. (1.2)] and POP [Eq. (1.3)] of QDT become nonequivalent due to the different approximation schemes to the partial consideration of higher order contributions. It is further noticed that in many conventional used QDT, such as the generalized quantum master equation, Bloch-Redfield theory and Fokker-Planck equations, there involve not only... 

As discussed above, a cmcial aspect is the interaction of the reactant with the solvent. In a quantum theory, the solvent can be represented as a bath of harmonic... 

Fig. 3. Vibrational population distributions of N2 formed in associative desorption of N-atoms from ruthenium, (a) Predictions of a classical trajectory based theory adhering to the Born-Oppenheimer approximation, (b) Predictions of a molecular dynamics with electron friction theory taking into account interactions of the reacting molecule with the electron bath, (c) Born—Oppenheimer potential energy surface, (d) Experimentally-observed distribution. The qualitative failure of the electronically adiabatic approach provides some of the best available evidence that chemical reactions at metal surfaces are subject to strong electronically nonadiabatic influences. (See Refs. 44 and 45.)...

The brief review of the newest results in the theory of elementary chemical processes in the condensed phase given in this chapter shows that great progress has been achieved in this field during recent years, concerning the description of both the interaction of electrons with the polar medium and with the intramolecular vibrations and the interaction of the intramolecular vibrations and other reactive modes with each other and with the dissipative subsystem (thermal bath). The rapid development of the theory of the adiabatic reactions of the transfer of heavy particles with due account of the fluctuational character of the motion of the medium in the framework of both dynamic and stochastic approaches should be mentioned. The stochastic approach is described only briefly in this chapter. The number of papers in this field is so great that their detailed review would require a separate article. 

The book covers a variety of questions related to orientational mobility of polar and nonpolar molecules in condensed phases, including orientational states and phase transitions in low-dimensional lattice systems and the theory of molecular vibrations interacting both with each other and with a solid-state heat bath. Special attention is given to simple models which permit analytical solutions and provide a qualitative insight into physical phenomena. 

The ions are regarded as rigid balls moving in a liquid bath. It is assumed that the macroscopic laws of motion in a viscous medium hold, and that the electrostatic interaction is determined by the theory of continuous dielectrics. This assumption implies that the moving particles are large compared to the molecular structure of the liquid. The most successful results of continuous theories can be found in any textbook of physical chemistry Stokes , law for viscous motion, Einstein s derivation of the dependence of viscosity on the concentration... 

The quantum alternative for the description of the vibrational degrees of freedom has been commented by Westlund et al. (85). The comments indicate that, to get a reasonable description of the field-dependent electron spin relaxation caused by the quantum vibrations, one needs to consider the first as well as the second order coupling between the spin and the vibrational modes in the ZFS interaction, and to take into account the lifetime of a vibrational state, Tw, as well as the time constant,T2V, associated with a width of vibrational transitions. A model of nuclear spin relaxation, including the electron spin subsystem coupled to a quantum vibrational bath, has been proposed (7d5). The contributions of the T2V and Tw vibrational relaxation (associated with the linear and the quadratic term in the Taylor expansion of the ZFS tensor, respectively) to the electron spin relaxation was considered. The description of the electron spin dynamics was included in the calculations of the PRE by the SBM approach, as well as in the framework of the general slow-motion theory, with appropriate modifications. The theoretical predictions were compared once again with the experimental PRE values for the Ni(H20)g complex in aqueous solution. This work can be treated as a quantum-mechanical counterpart of the classical approach presented in the paper by Kruk and Kowalewski (161). 

In the language of control theory, Tr[p(0)P] is a kinematic critical point [87] if Eq. (4.159) holds, since Tr[e p(0)e- P] = Tr[p(0)P] + Tr(7/[p(0),P]) + O(H ) for a small arbitrary system Hamiltonian H. Since we consider p in the interaction picture, Eq. (4.159) means that the score is insensitive (in first order) to a bath-induced unitary evolution (i.e., a generalized Lamb shift) [88]. The purpose of this assumption is only to simplify the expressions, but it is not essential. Physically, one may think of a fast auxiliary unitary transformation that is applied initially in order to diagonalize the initial state in the eigenbasis of P. 

The parameter is the damping constant, and (n) is the mean number of reservoir photons. The quantum theory of damping assumes that the reservoir spectrum is flat, so the mean number of reservoir oscillators (n) = ( (O)bj(O j) = ( (1 / ) — 1) 1 in the yth mode is independent of j. Thus the reservoir oscillators form a thermal system. The case ( ) = 0 corresponds to vacuum fluctuations (zero-temperature heat bath). It is convenient to consider the quantum dynamics of the system (56)-(59) in the interaction picture. Then the master equation for the density operator p is given by... 

An alternative approach widely used in polyatomic molecule studies is based on the Golden Rule and a perturbative treatment of the anharmonic coupling (57,62). This approach is not much used for diatomic molecules. In the liquid O2 example cited above, the Hamiltonian must be expanded to 30th order or so to calculate the multiphonon emission rate. But for vibrations of polyatomic molecules, which can always find relatively low-order VER pathways for each VER step, perturbation theory is very useful. In the perturbation approach, the molecule s entire ladder of vibrational excitations is the system and the phonons are the bath. Only lower-order processes are ordinarily needed (57) because polyatomic molecules have many vibrations ranging from higher to lower frequencies and only a small number of phonons, usually one or two, are excited in each VER step. The usual practice is to expand the interaction Hamiltonian (qn, Q) in Equation (2) in powers of normal coordinates (57,62) ... 

The basic theoretical framework for understanding the rates of these processes is Fermi s golden rule. The solute-solvent Hamiltonian is partitioned into three terms one for selected vibrational modes of the solute, including the vibrational mode that is initially excited, one for all other degrees of freedom (the bath), and one for the interaction between these two sets of variables. One then calculates rate constants for transitions between eigenstates of the first term, taking the interaction term to lowest order in perturbation theory. The rate constants are related to Fourier transforms of quantum time-correlation functions of bath variables. The most common... 

In the BQD case the non-Poisson renewal condition is a property emerging from the interaction with a cooperative bath. We want to illustrate here another important case, although this is not of central importance for the main aim of this review. Research work done in the last 15 years proves also that the non-Poisson character of the system of interest, generated by internal dynamics, rather than by the interaction with an anomalous bath, creates problems in decoherence theory. Let us see why. 

The seasoned Debye-Hiickel (D-H) theory, put forth in 1923 [33,34] takes into account the contribution of the ionic electrostatic interactions to the free energy of a solution and provides a quantitative expression for the activity coefficients. The basic concept of the D-H theory is that the long-range Coulomb interaction between two individual ions bathed in a salt solution is mediated by mobile ions from the solution. The effective charges of a certain ion are decreased as the result of charge screening by the mobile counterions it follows that, at sufficient distance, the interaction between two ions decays exponentially. We briefly outline the main considerations and assumptions of the D-H model ... 

For a large particle in a fluid at liquid densities, there are collective hydro-dynamic contributions to the solvent viscosity r, such that the Stokes-Einstein friction at zero frequency is In Section III.E the model is extended to yield the frequency-dependent friction. At high bath densities the model gives the results in terms of the force power spectrum of two and three center interactions and the frequency-dependent flux across the transition state, and at low bath densities the binary collisional friction discussed in Section III C and D is recovered. However, at sufficiently high frequencies, the binary collisional friction term is recovered. In Section III G the mass dependence of diffusion is studied, and the encounter theory at high density exhibits the weak mass dependence. 

In Section III the encounter theory was applied to test particle-bath particle interactions to yield, with additional assumptions, the test particle transport projjerties. In Section IV the theory is applied to pair dissociation dynamics. This is just the inverse process to particle encounter and reaction, and the two are related by the equilibrium constant. This illustrates an advantage of the stochastic encounter theory of Section II. The use of the potential with a transition state (as shown in Fig. 1) partitions conhgura-tion space uniquely into bound pairs and free pairs such that the equilibrium constant is trivially evaluated. This overcomes many of the problems associated with diffusion-based theories in which dubious boundary conditions must be used to mimic chemical reaction and the possibility of redissociation. 

For noninteracting particles D b is + D, but as the particles approach each other, the relative diffusion coefficient becomes dependent on their spatial separation. In liquids for large particles this arises from hydrodynamic interactions ( bow waves ), while in the gas phase the particles screen each other from the bath collisions. For small particles the viscoelastic projjerties of the fluid will become important near contact. The solution of Eq. (2.23) applies only for sufficiently large friction where the relative motion on all length scales is diffusive. In the other limit of very low friction, the general result obtained from molecular theory is of the form... 

The CREAM theory is complicated because of the number of states involved, but the physical principles are straightforward. First it is assumed that the Langevin limit applies such that atoms A and B are more massive than those of bath M. Thus a collision of M with, say, A will not change the momentum of A significantly, but may result in a reorientation of the angular momentum such that its orientation relative to the AB axis is changed, that is, the electronic state is altered. Second it is assumed that a three-body collision involved the interaction of M with only one of the atoms, say A. The... 

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