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<p>This study presents a comprehensive theoretical investigation of the conformational landscape, thermodynamic, electronic, photophysical behavior, and radiative lifetime of the aniline monohydrated dimer cluster (An<sub>2</sub>W<sub>1</sub>) using DFT and TD-DFT approaches at the B3LYP/aug-cc-pVTZ level. Conformational analysis identified eight distinct conformers, with conformer 01 being the most stable due to strong O–H···N, N···O–H, and N–H···N hydrogen bonding interactions. Thermodynamic parameters revealed minimal variations across conformers, though conformer 01 exhibited the lowest dipole moment and entropy, confirming its high stability. Vibrational infrared (IR) analysis confirmed the existence of hydrogen bonding in conformer 01, with the calculated frequencies correlating closely with the experimental results. UV/Vis absorption spectra showed significant intramolecular charge transfer (ICT) transitions, with notable redshifts and large Stokes shifts, particularly in conformer 08, indicating twisted ICT states. Fluorescence and phosphorescence lifetimes were computed using oscillator strengths and transition energies, revealing that conformer 04 had the longest fluorescence lifetime (32.44&#xa0;ns), and conformer 07 exhibited the longest phosphorescence lifetime (9.924&#xa0;µs). These findings confirm that the position of water and weak non-covalent interactions significantly influence photophysical responses and excited-state dynamics. Frontier molecular orbital (FMO) and chemical reactivity descriptor analysis revealed a correlation between energy gap and chemical stability. NBO, QTAIM and RDG-NCI analyses further confirmed stabilizing donor–acceptor, H-bonding and van der Waals interactions. These findings offer comprehensive insight into the structure–property relationships of An<sub>2</sub>W<sub>1</sub> clusters and their potential in in molecular photonics and photophysical applications.</p>

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Theoretical insights into the structure, stability, and photophysical properties of aniline monohydrated dimer clusters (An2W1): a DFT and TD-DFT study

  • 期刊论文

  • 发表日期：

    2026年5月4日

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  • Md. Alauddin,
  • Mohammad Abdul Matin,
  • Zubair Hasan

摘要

This study presents a comprehensive theoretical investigation of the conformational landscape, thermodynamic, electronic, photophysical behavior, and radiative lifetime of the aniline monohydrated dimer cluster (An2W1) using DFT and TD-DFT approaches at the B3LYP/aug-cc-pVTZ level. Conformational analysis identified eight distinct conformers, with conformer 01 being the most stable due to strong O–H···N, N···O–H, and N–H···N hydrogen bonding interactions. Thermodynamic parameters revealed minimal variations across conformers, though conformer 01 exhibited the lowest dipole moment and entropy, confirming its high stability. Vibrational infrared (IR) analysis confirmed the existence of hydrogen bonding in conformer 01, with the calculated frequencies correlating closely with the experimental results. UV/Vis absorption spectra showed significant intramolecular charge transfer (ICT) transitions, with notable redshifts and large Stokes shifts, particularly in conformer 08, indicating twisted ICT states. Fluorescence and phosphorescence lifetimes were computed using oscillator strengths and transition energies, revealing that conformer 04 had the longest fluorescence lifetime (32.44 ns), and conformer 07 exhibited the longest phosphorescence lifetime (9.924 µs). These findings confirm that the position of water and weak non-covalent interactions significantly influence photophysical responses and excited-state dynamics. Frontier molecular orbital (FMO) and chemical reactivity descriptor analysis revealed a correlation between energy gap and chemical stability. NBO, QTAIM and RDG-NCI analyses further confirmed stabilizing donor–acceptor, H-bonding and van der Waals interactions. These findings offer comprehensive insight into the structure–property relationships of An2W1 clusters and their potential in in molecular photonics and photophysical applications.