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Theoretical Study of the Isotope Effect in Optical Rotation.

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The isotope effect in optical rotation (OR) is influenced by nuclear vibrations, not just electronic properties. Deuterium substitution in chiral molecules, especially those with polarizable heteroatoms, significantly alters OR through specific vibrational modes.

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Area of Science:

  • Computational chemistry
  • Physical organic chemistry
  • Spectroscopy

Background:

  • Optical rotation (OR) is a key property of chiral molecules, primarily driven by electronic effects.
  • Nuclear vibrations also contribute to OR, and this contribution can change with isotopic substitution.
  • Understanding these vibrational contributions is crucial for a complete picture of optical activity.

Purpose of the Study:

  • To investigate the isotope effect on optical rotation (OR) in chiral molecules using H → D substitutions.
  • To identify specific locations and vibrational modes that significantly impact the vibrational correction to OR.
  • To elucidate the electronic response and molecular orbital contributions to the isotope effect in OR.

Main Methods:

  • Utilized a test set of 50 small organic molecules, including three-membered rings with diverse heteroatoms and functional groups.
  • Performed theoretical simulations at the B3LYP/aug-cc-pVDZ level of theory.
  • Employed molecular orbital decomposition analysis to understand the electronic contributions to OR.

Main Results:

  • Molecules with polarizable heteroatoms (e.g., S, P) exhibited the largest changes in vibrational correction to OR upon isotopic substitution.
  • Deuterium substitution on hydrogens opposite the functional group often yielded the greatest change in OR.
  • H/D wagging modes and C vibrations were identified as major contributors to the isotope effect.

Conclusions:

  • The vibrational correction to OR is sensitive to isotopic substitution, particularly in molecules with polarizable heteroatoms.
  • Specific vibrational modes, especially wagging and C vibrations, significantly influence the isotope effect on OR.
  • The observed effects are linked to how these vibrations modulate electronic transitions involving diffuse electron densities around polarizable heteroatoms.