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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.
This separation of the electronic and vibrational wavefunctions is an expression of the Born–Oppenheimer approximation and is the fundamental assumption of the Franck–Condon principle. Combining these equations leads to an expression for the probability amplitude in terms of separate electronic space, spin and vibrational contributions:
The Born-Oppenheimer approximation is unsuited for describing the dihydrogen cation accurately enough to explain the results of precision spectroscopy. The full Schrödinger equation for this cation, without the approximation of clamped nuclei, is much more complex, but nevertheless can be solved numerically essentially exactly using a ...
This is the Born–Oppenheimer approximation introduced by Born and Oppenheimer in 1927. Pioneering applications of this in chemistry were performed by Rice and Ramsperger in 1927 and Kassel in 1928, and generalized into the RRKM theory in 1952 by Marcus who took the transition state theory developed by Eyring in 1935 into account.
This is justified by the large disparity between the mass of an electron, and the typical mass of a nucleus and leads to the Born–Oppenheimer approximation and the idea that the structure and dynamics of a chemical species are largely determined by nuclear motion on potential energy surfaces.
The reduction from a fully quantum description to a classical potential entails two main approximations. The first one is the Born–Oppenheimer approximation, which states that the dynamics of electrons are so fast that they can be considered to react instantaneously to the motion of their nuclei. As a consequence, they may be treated separately.
This is to be contrasted with the Jahn–Teller effect which occurs for polyatomic molecules in electronic states that allow vibration through a symmetric nonlinear configuration, where the electronic state is degenerate, and which further involves a breakdown of the Born-Oppenheimer approximation but here caused by the vibrational kinetic ...
Vibronic spectroscopy is a branch of molecular spectroscopy concerned with vibronic transitions: ... In accordance with the Born-Oppenheimer approximation, where ...