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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 nearly 200 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 electron is electrons are completely delocalized
Born-Oppenheimer Approximation
(compactly)
• Adiabatic behavior
– Rapid and smooth adjustments of the electrons
• For any particular electronic state the wave function for the full
Hamiltonian is approximated as �= χ(R)ψ(r;R)
• <ψ(r;R)|H|�> = E<ψ(r;R)|�> 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