In quantum chemistry and molecular physics, the Born–Oppenheimer (BO) approximation is the best-known mathematical approximation in molecular dynamics. Specifically, it is the assumption that the wave functions of atomic nuclei and electrons in a molecule can be treated separately, based on the fact that the nuclei are much heavier than the electrons. Due to the larger relative mass of a nucleus compared to an electron, the coordinates of the nuclei in a system are approximated as fixed, while the coordinates of the electrons are dynamic.^[1] The approach is named after Max Born and his 23-year-old graduate student J. Robert Oppenheimer, the latter of whom proposed it in 1927 during a period of intense ferment in the development of quantum mechanics.^[2][3]

The approximation is widely used in quantum chemistry to speed up the computation of molecular wavefunctions and other properties for large molecules. There are cases where the assumption of separable motion no longer holds, which make the approximation lose validity (it is said to "break down"), but even then the approximation is usually used as a starting point for more refined methods.

In molecular spectroscopy, using the BO approximation means considering molecular energy as a sum of independent terms, e.g.:

These terms are of different orders of magnitude and the nuclear spin energy is so small that it is often omitted. The electronic energies ${\displaystyle E_{\text{electronic}}}$ consist of kinetic energies, interelectronic repulsions, internuclear repulsions, and electron–nuclear attractions, which are the terms typically included when computing the electronic structure of molecules.

Example

The benzene molecule consists of 12 nuclei and 42 electrons. The Schrödinger equation, which must be solved to obtain the energy levels and wavefunction of this molecule, is a partial differential eigenvalue equation in the three-dimensional coordinates of the nuclei and electrons, giving 3 × 12 = 36 nuclear + 3 × 42 = 126 electronic = 162 variables for the wave function. The computational complexity, i.e., the computational power required to solve an eigenvalue equation, increases faster than the square of the number of coordinates.^[4]

When applying the BO approximation, two smaller, consecutive steps can be used: For a given position of the nuclei, the electronic Schrödinger equation is solved, while treating the nuclei as stationary (not "coupled" with the dynamics of the electrons). This corresponding eigenvalue problem then consists only of the 126 electronic coordinates. This electronic computation is then repeated for other possible positions of the nuclei, i.e. deformations of the molecule. For benzene, this could be done using a grid of 36 possible nuclear position coordinates. The electronic energies on this grid are then connected to give a potential energy surface for the nuclei. This potential is then used for a second Schrödinger equation containing only the 36 coordinates of the nuclei.

So, taking the most optimistic estimate for the complexity, instead of a large equation requiring at least ${\displaystyle 162^{2}=26\,244}$ hypothetical calculation steps, a series of smaller calculations requiring ${\displaystyle 126^{2}N=15\,876\,N}$ (with N being the number of grid points for the potential) and a very small calculation requiring ${\displaystyle 36^{2}=1296}$ steps can be performed. In practice, the scaling of the problem is larger than ${\displaystyle n^{2}}$, and more approximations are applied in computational chemistry to further reduce the number of variables and dimensions.

The slope of the potential energy surface can be used to simulate molecular dynamics, using it to express the mean force on the nuclei caused by the electrons and thereby skipping the calculation of the nuclear Schrödinger equation.

Detailed description

The BO approximation recognizes the large difference between the electron mass and the masses of atomic nuclei, and correspondingly the time scales of their motion. Given the same amount of momentum, the nuclei move much more slowly than the electrons. In mathematical terms, the BO approximation consists of expressing the wavefunction (${\displaystyle \Psi _{\mathrm {total} }}$) of a molecule as the product of an electronic wavefunction and a nuclear (vibrational, rotational) wavefunction. ${\displaystyle \Psi _{\mathrm {total} }=\psi _{\mathrm {electronic} }\psi _{\mathrm {nuclear} }}$. This enables a separation of the Hamiltonian operator into electronic and nuclear terms, where cross-terms between electrons and nuclei are neglected, so that the two smaller and decoupled systems can be solved more efficiently.

In the first step the nuclear kinetic energy is neglected,^{[note 1]} that is, the corresponding operator T_n is subtracted from the total molecular Hamiltonian. In the remaining electronic Hamiltonian H_e the nuclear positions are no longer variable, but are constant parameters (they enter the equation "parametrically"). The electron–nucleus interactions are not removed, i.e., the electrons still "feel" the Coulomb potential of the nuclei clamped at certain positions in space. (This first step of the BO approximation is therefore often referred to as the clamped-nuclei approximation.)

The electronic Schrödinger equation

${\displaystyle H_{\text{e}}(\mathbf {r} ,\mathbf {R} )\chi (\mathbf {r} ,\mathbf {R} )=E_{\text{e}}\chi (\mathbf {r} ,\mathbf {R} )}$

where ${\displaystyle \chi (\mathbf {r} ,\mathbf {R} )}$ is the electronic wavefunction for given positions of nuclei (fixed R), is solved approximately.^{[note 2]} The quantity r stands for all electronic coordinates and R for all nuclear coordinates. The electronic energy eigenvalue E_e depends on the chosen positions R of the nuclei. Varying these positions R in small steps and repeatedly solving the electronic Schrödinger equation, one obtains E_e as a function of R. This is the potential energy surface (PES): ${\displaystyle E_{e}(\mathbf {R} )}$. Because this procedure of recomputing the electronic wave functions as a function of an infinitesimally changing nuclear geometry is reminiscent of the conditions for the adiabatic theorem, this manner of obtaining a PES is often referred to as the adiabatic approximation and the PES itself is called an adiabatic surface.^{[note 3]}

In the second step of the BO approximation the nuclear kinetic energy T_n (containing partial derivatives with respect to the components of R) is reintroduced, and the Schrödinger equation for the nuclear motion^{[note 4]}

${\displaystyle \phi (\mathbf {R} )=E\phi (\mathbf {R} )}$

is solved. This second step of the BO approximation involves separation of vibrational, translational, and rotational motions. This can be achieved by application of the Eckart conditions. The eigenvalue E is the total energy of the molecule, including contributions from electrons, nuclear vibrations, and overall rotation and translation of the molecule.^{[clarification needed]} In accord with the Hellmann–Feynman theorem, the nuclear potential is taken to be an average over electron configurations of the sum of the electron–nuclear and internuclear electric potentials.

Derivation

It will be discussed how the BO approximation may be derived and under which conditions it is applicable. At the same time we will show how the BO approximation may be improved by including vibronic coupling. To that end the second step of the BO approximation is generalized to a set of coupled eigenvalue equations depending on nuclear coordinates only. Off-diagonal elements in these equations are shown to be nuclear kinetic energy terms.

It will be shown that the BO approximation can be trusted whenever the PESs, obtained from the solution of the electronic Schrödinger equation, are well separated:

${\displaystyle E_{0}(\mathbf {R} )\ll E_{1}(\mathbf {R} )\ll E_{2}(\mathbf {R} )\ll \cdots {\text{ for all }}\mathbf {R} }$.

We start from the exact non-relativistic, time-independent molecular Hamiltonian:

${\displaystyle H=H_{\text{e}}+T_{\text{n}}}$

with

${\displaystyle H_{\text{e}}=-\sum _{i}{{\frac {1}{2}}\nabla _{i}^{2}}-\sum _{i,A}{\frac {Z_{A}}{r_{iA}}}+\sum _{i>j}{\frac {1}{r_{ij}}}+\sum _{B>A}{\frac {Z_{A}Z_{B}}{R_{AB}}}\quad {\text{and}}\quad T_{\text{n}}=-\sum _{A}{{\frac {1}{2M_{A}}}\nabla _{A}^{2}}.}$

The position vectors ${\displaystyle \mathbf {r} \equiv \{\mathbf {r} _{i}\}}$ of the electrons and the position vectors ${\displaystyle \mathbf {R} \equiv \{\mathbf {R} _{A}=(R_{Axy},R_{Ayz},R_{Azx})\}}$ of the nuclei are with respect to a Cartesian inertial frame. Distances between particles are written as ${\displaystyle r_{iA}\equiv |\mathbf {r} _{i}-\mathbf {R} _{A}|}$ (distance between electron i and nucleus A) and similar definitions hold for ${\displaystyle r_{ij}}$ and ${\displaystyle R_{AB}}$.

We assume that the molecule is in a homogeneous (no external force) and isotropic (no external torque) space. The only interactions are the two-body Coulomb interactions among the electrons and nuclei. The Hamiltonian is expressed in atomic units, so that we do not see Planck's constant, the dielectric constant of the vacuum, electronic charge, or electronic mass in this formula. The only constants explicitly entering the formula are Z_A and M_A – the atomic number and mass of nucleus A.

It is useful to introduce the total nuclear momentum and to rewrite the nuclear kinetic energy operator as follows:

${\displaystyle T_{\text{n}}=\underset{A}{\sum <!--\; \sum \; -->}\underset{\mathrm{\alpha <!--\; \alpha \; -->}=x,y,z}{\sum <!--\; \sum \; -->}\frac{P_{A\mathrm{\alpha <!--\; \alpha \; -->}}{P}_{A\mathrm{\alpha <!--\; \alpha \; -->}}}{2M_A}\text{with}{P}_{A\mathrm{\alpha <!--\; \alpha \; -->}}=-<!--\; -\; -->i\frac{\mathrm{\partial <!--\; \partial \; -->}}{\mathrm{\partial <!--\; \partial \; -->}{R}_{}}}$Zdroj:https://en.wikipedia.org?pojem=Born–Oppenheimer_approximation
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