Born-Oppenheimer approximation dynamic

The first requirement is the definition of a low-dimensional space of reaction coordinates that still captures the essential dynamics of the processes we consider. Motions in the perpendicular null space should have irrelevant detail and equilibrate fast, preferably on a time scale that is separated from the time scale of the essential motions. Motions in the two spaces are separated much like is done in the Born-Oppenheimer approximation. The average influence of the fast motions on the essential degrees of freedom must be taken into account this concerns (i) correlations with positions expressed in a potential of mean force, (ii) correlations with velocities expressed in frictional terms, and iit) an uncorrelated remainder that can be modeled by stochastic terms. Of course, this scheme is the general idea behind the well-known Langevin and Brownian dynamics. 

Use of the Born-Oppenheimer approximation is implicit for any many-body problem involving electrons and nuclei as it allows us to separate electronic and nuclear coordinates in many-body wave function. Because of the large difference between electronic and ionic masses, the nuclei can be treated as an adiabatic background for instantaneous motion of electrons. So with this adiabatic approximation the many-body problem is reduced to the solution of the dynamics of the electrons in some frozen-in configuration of the nuclei. However, the total energy calculations are still impossible without making further simplifications and approximations. 

Central to the modern approach to chemical reactivity as dynamics on a potential energy surface, is the Born-Oppenheimer approximation.9... 

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 basic problem is to solve the time-independent electronic Schrodinger equation. Since the mass of the electrons is so small compared to that of the nuclei, the dynamics of nuclei and electrons can normally be decoupled, and so in the Born-Oppenheimer approximation the many-electron wavefunction P and corresponding energy may be obtained by solving the time-independent Schrodinger equation in which the nuclear positions are fixed. We thus solve... 

Molecular Dynamics Beyond the Born-Oppenheimer Approximation. 

We wanted to extend this approach to include dynamical effects on line shapes. As discussed earlier, for this approach one needs a trajectory co t) for the transition frequency for a single chromophore. One could extract a water cluster around the HOD molecule at every time step in an MD simulation and then perform an ab initio calculation, but this would entail millions of such calculations, which is not feasible. Within the Born Oppenheimer approximation the OH stretch potential is a functional of the nuclear coordinates of all the bath atoms, as is the OH transition frequency. Of course we do not know the functional. Suppose that the transition frequency is (approximately) a function of a one or more collective coordinates of these nuclear positions. A priori we do not know which collective coordinates to choose, or what the function is. We explored several such possibilities, and one collective coordinate that worked reasonably well was simply the electric field from all the bath atoms (assuming the point charges as assigned in the simulation potential) on the H atom of the HOD molecule, in the direction of the OH bond. 

H. Koppel, W. Domcke, and L. S. Cederbaum, Multimode molecular dynamics beyond the Born-Oppenheimer approximation, Adv. Chem. Phys. 57, 59-246(1984). 

The well-known Born-Oppenheimer approximation (BOA) assumes all couplings Kpa between the PES are identically zero. In this case, the dynamics is described simply as nuclear motion on a single adiabatic PES and is the fundamental basis for most traditional descriptions of chemistry, e.g., transition state theory (TST). Because the nuclear system remains on a single adiabatic PES, this is also often referred to as the adiabatic approximation. 

A full theoretical treatment of Pgl within the Born-Oppenheimer approximation involves two stages. First, the potentials V (R), V+(R), and the width T(f ) of the initial state must be calculated in electronic-structure calculations at different values of the internuclear distance R—within the range relevant for an actual collision at a certain collision energy—and then, in the second stage the quantities observable in an experiment (e.g., cross sections, energy and angular distributions of electrons) must be calculated from the functions V+(R), V+(R), and T(f ), taking into account the dynamics of the heavy-particle collisions. 

Consider now the influence of the high-frequency fluctuations in the environment only (is 3> B). Since the frequencies of the fluctuations are much higher than the typical spin-dynamics frequencies, one may eliminate these high-frequency fluctuations using the adiabatic (Born-Oppenheimer) approximation, as described, e.g., by Leggett et al. [8]. 

Electronic and optical properties of complex systems are now accessible thanks to the impressive development of theoretical approaches and of computer power. Surfaces, nanostructures, and even biological systems can now be studied within ab-initio methods [53,54]. In principle within the Born-Oppenheimer approximation to decouple the ionic and electronic dynamics, the equation that governs the physics of all those systems is the many-body equation ... 

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