波谱分析课件 chapter 2 UV-vis.pptVIP

Chapter 2 Ultraviolet and Visible Absorption Spectroscopy (UV-Vis) At room temperature, most of the atoms, molecules and electrons are in the lowest energy orbital called ground state.? The electron of atom (molecule) at ground state can absorb proton and transit to higher energy orbital called excited state. Atom or molecule can absorb the radiation only when the energy of proton is equal to the energy difference of the two orbitals 2.1 Basic principles of UV-vis Ultraviolet-visible spectroscopy corresponds to excitations of outer shell electron between the energy levels that correspond to the molecular orbital of the systems.? The band spectrum of molecule due to vibrational and rotational levels Comparing: Atomic spectrum 2.2 Molecular orbitals and electronic transition While two atoms form chemical bond, their atomic orbital combine together to form molecular orbital. Bonding orbital and antibonding orbital Bonding orbital energy level is always lower than that of the original atomic orbital Antibonding orbital energy - higher s , p orbitals and h electrons Types of Electronic Transitions Transitions involving p, s, and n electrons Transitions involving charge-transfer electrons Transitions involving d and f electrons (not covered in this Unit) Absorbing species containing p, s, and n electrons Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy. The spectrum of a molecule containing these chromophores is complex. This is because the superposition of rotational and vibrational transitions on the electronic transitions gives a combination of overlapping lines. This appears as a continuous absorption band. s - s* Transitions An electron in a bonding s orbital is excited to the corresponding antibonding orbital. The energy required is large. For example, methane (which has only C-H bonds, and can only u