Born Oppenheimer Approximation

Learn all about this fundamental concept in quantum mechanics, including its historical origins, key principles, and applications.

SS by Sreyansu Satpathy
Introduction to Born Oppenheimer Approximation
Born Oppenheimer Approximation (BOA) is a widely used theoretical model in quantum mechanics that separates the electronic and
nuclear components of the quantum problem of molecules. This separation allows for the calculation of the electronic structure while
keeping the nuclear positions fixed, which is a great simplification that can provide insight into chemical bonding.

"The separation of electronic and nuclear motion is a truly profound idea, for it allows us to first consider the motion of the
electrons, independently of what the nuclei are doing, and then to consider how the nuclei move in response to the motion of the
electrons." - P.W. Atkins
Historical background and development
The Born-Oppenheimer Approximation was first introduced in 1927 by the physicists Max Born and Robert Oppenheimer. It was
invented as part of the quantum mechanics revolution that was taking place at the time. With the BOA, Born and Oppenheimer were
able to solve the Schrödinger equation for the hydrogen molecule ion (H2+), which was a major breakthrough in the field.

Max Born Robert Oppenheimer

Born was a German physicist and mathematician who made Oppenheimer was an American physicist and professor who is
major contributions to quantum mechanics, solid-state best known for his contributions to the Manhattan Project
physics, and optics. during World War II.
Key principles and assumptions
The BOA makes several key assumptions, including the separation of nuclear and electronic motion, the use of the Born-
Oppenheimer potential energy surface, and the assumption that the electronic motion is faster than the nuclear motion (adiabatic
approximation). These assumptions make the BOA less accurate in some cases, such as when dealing with highly excited states or
reactive systems, but it is still a useful and widely used model.

1 Assumption 1: Separation of nuclear and 2 Assumption 2: Born-Oppenheimer potential

electronic motion energy surface

The BOA separates the motion of the electrons and The potential energy surface represents the energy of
nuclei, treating the electrons as being in a fixed the system as a function of the nuclear coordinates, and
potential created by the nuclei. is essential for the calculations of molecular properties.
Applications of BO Approximation in quantum mechanics
BOA is a key tool in computational chemistry, allowing for the prediction of chemical properties and reactions. It has many applications in areas such as drug
design and materials science. Scientists also use the BOA in studies of molecular dynamics and spectroscopy to understand how molecules move and interact.

BOA can be applied to predict the structure and properties of molecules like Computational chemistry techniques that use the BOA can help researchers
the one shown here. in drug design and other areas.
Challenges and limitations of BO Approximation
The BOA has several challenges and limitations. For instance, it can be less accurate than other theoretical models in certain cases.
At the same time, the BOA provides important insights into the nature of molecular bonding. Researchers continually refine and
improve on the BOA, creating new theoretical models and computational tools to help predict and understand molecular behaviour.

Challenge or Limitation Description

Accuracy The BOA can be less accurate than other theoretical models
when dealing with highly excited states or reactive systems.

Computational cost Calculations using the BOA can be computationally

expensive and can require a lot of time and resources.
Comparison with other theoretical models in chemical
physics
BOA is not the only model used in quantum chemistry. Other theoretical models such as density functional theory (DFT), Hartree-Fock and
coupled cluster theory (CC) also provide important insights into the nature of chemical bonding. Each model has its own strengths and
weaknesses, and each is more appropriate for different types of problems.

Model Model Model

Density functional theory (DFT) Hartree-Fock Coupled cluster theory (CC)

DFT is a widely used technique that is Hartree-Fock is an earlier and simpler CC is a more accurate and
more computationally efficient than other model than BOA, but it is still used in computationally expensive technique
models, making it well suited for large some situations, particularly for small than BOA, but it is more difficult to
molecules and materials molecules. apply and less widely used.
Conclusion and future directions
The BOA is an important theoretical model in quantum mechanics that provides valuable insights into chemical bonding and
molecular behavior. While it has challenges and limitations, it remains an essential tool in computational chemistry and spectroscopy.
As technology continues to improve and scientists develop new theoretical models, the BOA will continue to evolve and improve,
allowing us to better understand the nature of chemical bonding and molecular behaviour.