12.3
Molecular Spectroscopy: Absorption and Emission
Molecules possess discrete energy levels called quantum states. Unlike atoms, which have simpler energy levels, molecules possess additional rotationa…
In a molecule, discrete energy states called quantum states exist. Each quantum state—be it electronic, vibrational, or rotational—is unique, with a definite energy value, and separated from others of its type by energy gaps.
On absorbing a photon of electromagnetic radiation, a molecule can be excited to a higher energy level. As a result, it undergoes relaxation to a lower energy level by emitting a photon.
The molecule can only absorb or emit photons of specific energies that match the energy gaps between these energy levels. So, each transition is frequency- or wavelength-dependent.
Accordingly, different kinds of excitation occur in a molecule, depending on the radiation wavelength.
For example, photons in the microwave region are absorbed to alter internal bond rotation, while those in the infrared region possess the energy required to change the frequency of bond vibrations.
Photons in the UV–visible range can excite electrons to higher electronic energy states.
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Q1: What are quantum states in molecules?
Quantum states are discrete energy levels that exist in molecules, each with a definite energy value. These states can be electronic, vibrational, or rotational, and are separated from one another by specific energy gaps. Unlike continuous energy, molecules can only occupy these distinct quantum states, making energy absorption and emission frequency-dependent processes.
Q2: How does a molecule absorb and emit photons?
A molecule absorbs a photon of electromagnetic radiation when its energy matches the gap between two quantum states, exciting the molecule to a higher energy level. When the excited molecule returns to a lower energy state, it emits a photon with energy equivalent to that gap. This process ensures each transition is wavelength- or frequency-dependent, allowing only specific photons to be absorbed or emitted.
Q3: Why do different wavelengths of radiation affect molecules differently?
Different radiation wavelengths correspond to different energy levels in molecules. Microwave photons possess energy to alter internal bond rotation, infrared photons change bond vibration frequencies, and ultraviolet and visible photons can excite electrons to higher electronic energy states. The varying magnitudes of energy gaps between rotational, vibrational, and electronic levels determine which wavelengths are absorbed during each type of transition.
Q4: What is the relationship between energy gaps and photon wavelength?
The energy of an absorbed or emitted photon is equivalent to the energy gap between two quantum states involved in a molecular transition. Since photon energy is inversely related to wavelength, larger energy gaps require shorter wavelengths and higher-frequency radiation. This direct relationship ensures that each specific transition in a molecule corresponds to a unique wavelength of electromagnetic radiation.
Q5: What types of molecular changes occur during photon absorption?
When a molecule absorbs a photon, three types of changes can occur depending on the radiation energy: rotation around a bond can change, the frequency of bond vibration can increase, or an electron can transition from its ground state to an excited state. Molecules with conjugated double bonds are particularly susceptible to electronic excitation by ultraviolet and visible photons.
Q6: How do electronic, vibrational, and rotational energy levels differ in molecules?
Molecules possess three distinct types of energy levels: electronic, vibrational, and rotational. Each type has its own set of discrete quantum states separated by characteristic energy gaps. The energy gaps between electronic levels are largest, followed by vibrational gaps, and then rotational gaps, which are smallest. These differences determine which wavelengths of radiation interact with each type of molecular motion.
Q7: Why must photon energy match specific molecular transitions?
Molecules can only absorb or emit photons whose energy exactly matches the energy gap between two quantum states. This quantized nature of molecular energy means that photons with incorrect energy cannot cause transitions. The specificity of this matching process is fundamental to spectroscopy and explains why molecular electronic transitions occur only at particular wavelengths.