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<p>This study investigates how changes in vibrational frequencies upon electronic transition (the squeezing effect) affect internal conversion rate constant (<i>k</i><sub>IC</sub>) calculations in an indocyanine molecule. Results obtained demonstrate that the squeezing effect alters <i>k</i><sub>IC</sub> by only 0.38%, making it negligible. This occurs because the modes with significant frequency shifts (12–55%) are low-frequency (&lt; 100 cm<sup>–1</sup>) and contribute minimally to <i>k</i><sub>IC</sub>, while the modes that dominate <i>k</i><sub>IC</sub> exhibit negligible frequency shifts (1–2%). Notably, the Lagrange multiplier technique incorrectly estimates <i>k</i><sub>IC</sub> for molecules with low-frequency modes that have large Huang–Rhys factors, since such modes undergo substantial frequency shifts.</p>

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Effect of vibrational frequency shifts on internal conversion rate constant calculations

  • 期刊论文

  • 发表日期：

    2026年6月23日

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  • L. I. Valiulina,
  • R. Valiyev,
  • V. N. Cherepanov,
  • V. P. Tuguldurova

摘要

This study investigates how changes in vibrational frequencies upon electronic transition (the squeezing effect) affect internal conversion rate constant (kIC) calculations in an indocyanine molecule. Results obtained demonstrate that the squeezing effect alters kIC by only 0.38%, making it negligible. This occurs because the modes with significant frequency shifts (12–55%) are low-frequency (< 100 cm–1) and contribute minimally to kIC, while the modes that dominate kIC exhibit negligible frequency shifts (1–2%). Notably, the Lagrange multiplier technique incorrectly estimates kIC for molecules with low-frequency modes that have large Huang–Rhys factors, since such modes undergo substantial frequency shifts.