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When light passes through a substance, a portion of the light is absorbed while the remaining light is reflected or transmitted. If the molecule absorbs light between the wavelengths of 180–400 nm range, the UV spectrum is obtained, and if it absorbs light in the 400–780 nm wavelength range, the visible spectrum is obtained.

The UV–Vis spectrum of a molecule is the plot of its absorbance versus wavelength. The plot is drawn by taking molar absorptivity (ε) or log ε on the y-axis (ordinate) and wavelength on the x-axis (abscissa). Absorbance values represent light absorption by the molecule and cannot exceed 100 percent. When the absorbance is plotted against wavelength, the wavelength at which the molecule shows the maximum absorbance is called λmax. Since absorption occurs at a broad wavelength, it is often called an absorption band rather than a single peak.

Peaks in the UV–Vis spectrum vary in height and width based on molecular structure, electronic transitions, and solvent interactions.

  1. Molecular Structure: Different structures, like conjugated double bonds (alternating single and double bonds), have smaller energy gaps between their molecular orbitals. This means they absorb light at longer wavelengths, often in the visible range. As a result, the structure of the molecule can shift the peak to higher or lower wavelengths and change its intensity.
  2. Electronic Transitions: Various electron transitions (e.g., π → π*, n → π*) absorb light differently, influencing peak strength. Molecules with π (pi) bonds or nonbonding (n) electron pairs can exhibit multiple types of transitions, leading to different peaks or bands in the spectrum.
  3. Solvent Effects: The solvent in which the molecule is dissolved can also affect the spectrum. When a molecule interacts with a solvent, it can alter the molecule's electronic environment, sometimes stabilizing or destabilizing certain molecular orbitals. This solvent effect can cause shifts in the peak position and may alter the peak's intensity.

These factors often result in broadened bands instead of single peaks, reflecting the molecule's complex behavior in different conditions.

From Chapter 12:

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