Born-Oppenheimer

Approximation
&
Potential Energy Surface
Elizabeth Harrison
History and Caveat
• Named after Max Born and J. Robert Oppenheimer
– University of Göttingen (1927)

• Many-atom systems that have enough energy to undergo a chemical

change
• Same electronic state throughout its time evolution
– Electronic energy is the potential for the nuclear motion

• Approximation: the concept of a unique potential function governing the

motion of the atoms
Introduction
• Allows us to understand the geometrical structure of a molecule at
equilibrium and also for small vibrations about equilibrium
• It allows us to compute the electronic structure of a molecule without
saying anything about the quantum mechanics of the nuclei
• Electron is lighter by a factor of 2000 or more than the nucleus
• Potential remains the same under isotopic substitution
• 2 assumptions
– From the point of the electron, the nucleus is fixed
– From the point of the nucleus, the electrons are completely delocalized
Molecular Hamiltonian

(compactly)

(clamped nuclei Schrödinger equation)

Born-Oppenheimer Approximation

෡ = 𝐸𝛹
• 𝐻𝛹
− Nuclear and electronic

− 𝛹 for nuclear being the product of translation, rotation, and vibration

Diagonalization of Hamiltonian
• Diagonalize the electronic Hamiltonian
– Hel 𝛹(r,R) = Eel(R)𝛹(r,R)
– One electronic state
– Lowest eigenvalue

• Repeated at other values of R to yield the electronic states and their

energies as a function of R
– Lowest electronic energy for an entire range of configurations of the nuclei

• Adiabatic behavior
– Rapid and smooth adjustments of the electrons
• For any particular electronic state the wave function for the full
Hamiltonian is approximated as 𝛹= χ(R)ψ(r;R)
• <ψ(r;R)|H|𝛹> = E<ψ(r;R)|𝛹> to (T + Eel(R))χ(R) = Eχ(R)
– Electronic energy plays the role of the potential for the motion of the nuclei
– T is the kinetic energy operator for the relative motion of the nuclei
– Approximation fails when the matrix element of T between two different electronic
states is not small
Potential Energy Surfaces
• Built from solving the motion of the electrons for the nuclear
configurations, giving an electronic energy Ee(R)and wavefunctionΨ(r;R)
• Internal coordinates
– 3N (x, y, z)

• Stationary points
– Gradients with respect to all internal coordinates are zero

• Minima
• Saddle points
• Transition states
• A + BC > AB + C
• Reaction coordinate
• Energy increases if we deviate from
the reaction coordinate
• Maximum
• Asymmetric stretch motion of A-B-C
• Solid lines are contours of given
potential energy
• Minimum reaction path
• Entrance valley
• BC: dissociation energy
Born-Oppenheimer Diagonal Correction

• Also called adiabatic correction

References
• Engel, T.; Reid, P.; Hehre, W. Physical chemistry; Pearson: Boston, Mass,
2013; pp. 537-538.
• Levine, R. Molecular Reaction Dynamics; Cambridge University Press:
Cambridge, 2009; pp. 148-152.
• Mustroph, H. “Potential-Energy Surfaces, the Born-Oppenheimer
Approximations, and the Franck-Condon Principle: Back to the Roots,”
ChemPhysChem 2016, 17, 2616-2629.
• Sherrill, C. The Born-Oppenheimer Approximation; Georgia Institute of
Technology: Georgia, 2005.
• Simmons, J.; Nichols, J. The Born-Oppenheimer Separation of Electronic
and Nuclear Motions
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistr
y_Textbook_Maps/Book%3A_Quantum_Mechanics__in_Chemistry_(Simon
s_and_Nichols)/3%3A_Nuclear_Motion/3.01%3A_The_Born-
Oppenheimer_Separation_of_Electronic_and_Nuclear_Motions.