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Hydrogen Atom in Quantum Chemistry
Hydrogen Atom in Quantum Chemistry
One particle moving under a central force. CENTRAL FORCE Derive from potential energy function ,function only of distance of particle from origin. Spherically symmetry. V=v(r)
The relation between force (F) and potential (P). Since V is the function only on r Hence The equation become
Gives the operator for square of magnitude of orbital angular momentum of a single particle L^2. The Hamiltonian becomes
In classical mechanics a particle subject to a central force has angular momentum conserve. In quantum mechanics has definite values for both energy and angular momentum. The commutator of H and L must be vanish.
Set the simultaneous eigenfunction of , L^ and L^2 for a central-force problem. Let the denote of these common eigentfunction.
The solution of separation variables, we setting When the system is composed of two no interacting particles, we can reduce two-particle problem into two separate one particle problem by In general can solve any number of non interacting particles. For n such particles, we have
For system of non interacting particles, the energy is the sum of the individual energies of each particle and wave function is the product of wave functions for each particles. This result also apply to single particle whose Hamiltonian is the sum of separate term for each coordinate
We can draw vector R like this The kinetic energy is the sum of kinetic energy of two particle Let M is total mass and m is reduce mass
Then the 1st term is the kinetic energy due to translational motion of the whole system of mass M. The quantity of kinetic energy of mass M at the centre of mass. note: translational is motion at the same displacement. The 2nd term is kinetic energy of internal motion of two particles. (vibration and rotation)
The Hamiltonian function is The quantum-mechanical energy is So the translational energy E found by solving Schrdinger equation And the E can be found using the Schrdinger equation
M
Hydrogen like atom is the most important system in QM. Schrdinger equation for atom with more than one electron cant be obtained- interelectronic repulsion. So we assume no repulsion so electron can be treated independently. Atomic wave function will be approximate by a product of one electron function.
A one-electron wave function is called orbital. An orbital for an electron in an atom is called atomic orbital. Atomic orbital's is use to construct approximate wave function for many-electron atoms or for wave function for molecule.
Degeneracy
For bound state(transition state), the energy depends only on n. but wavefunction depend on all three quantum number n, l, and m. n = 1, 2, 3, .. l = 0, 1, 2, 3, ,n 1 m = -l, -1, +10l 1 , l
Degeneracy - when different value of l or m but have same value of n and have the same energy. Except for n = 1. For each value of l, the value of m is 2l+1. The degree of degeneracy of bound state level of hydrogen like atom for discreet level is found n square. For continuum levels for a given energy there is no restriction on the maximum value of l hence these levels are infinity-fold degenerate. (no discreet).
The bound energy of hydrogen like atom is discrete. The change in n are allowed so the wave number of hydrogen spectral lines are