Rotation ,vibration, electronic spectra - Texas Aamp;M University 旋转，振动，电子光谱-德克萨斯amp；M大学.pptVIP

Rotation and vibration spectra Rotational States Molecular spectroscopy: We can learn about molecules by studying how molecules absorb, emit, and scatter electromagnetic radiation. From the equipartition theorem, the N2 molecule may be thought of as two N atoms held together with a massless, rigid rod (rigid rotator model). In a purely rotational system, the kinetic energy is expressed in terms of the angular momentum L and rotational inertia I. Rotational States L is quantized. The energy levels are Erot varies only as a function of the quantum number l. Vibrational States There is the possibility that a vibrational energy mode will be excited. No thermal excitation of this mode in a diatomic gas at ordinary temperature. It is possible to stimulate vibrations in molecules using electromagnetic radiation. Assume that the two atoms are point masses connected by a massless spring with simple harmonic motion: Vibrational States The energy levels are those of a quantum-mechanical oscillator. The frequency of a two-particle oscillator is Where the reduced mass is μ = m1m2 / (m1 + m2) and the spring constant is κ. If it is a purely ionic bond, we can compute κ by assuming that the force holding the masses together is Coulomb. and Vibration and Rotation Combined It is possible to excite the rotational and vibrational modes simultaneously. Total energy of simple vibration-rotation system: Vibrational energies are spaced at regular intervals. emission features due to vibrational transitions appear at regular intervals: ??ω, 3/2?ω, etc. Transition from l + 1 to l: Photon will have an energy An emission-spectrum spacing that varies with l The higher the starting energy level, the greater the photon energy. Vibrational energies are greater than rotational energies. This energy difference results in the band spectrum. Typical section of the emission spectrum of a diatomic molecule. Equally spaced groups of lines correspond to the equal spacings betwe