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Journal of Chemical Sciences

, Volume 128, Issue 8, pp 1175–1189 | Cite as

On the Attosecond charge migration in Cl…..N, Cl…..O, Br…..N and Br…..O Halogen-bonded clusters: Effect of donor, acceptor, vibration, rotation, and electron correlation

  • SANKHABRATA CHANDRA
  • MOHAMMED MUSTHAFA IQBAL
  • ATANU BHATTACHARYAEmail author
Article

Abstract

The electron-electron relaxation and correlation-driven charge migration process, which features pure electronic aspect of ultrafast charge migration phenomenon, occurs on a very short timescale in ionized molecules and molecular clusters, prior to the onset of nuclear motion. In this article, we have presented nature of ultrafast pure electronic charge migration dynamics through Cl…..N, Cl…..O, Br…..N, and Br…..O halogen bonds, explored using density functional theory. We have explored the role of donor, acceptor, electron correlation, vibration and rotation in charge migration dynamics through these halogen bonds. For this work, we have selected ClF, Cl2, ClOH, ClCN, BrF, BrCl, BrOH, and BrCN molecules paired with either NH3 or H2O. We have found that the timescale for pure electron-electron relaxation and correlation-driven charge migration through the Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonds falls in the range of 300–600 attosecond. The primary driving force behind the attosecond charge migration through the Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonds is the energy difference (ΔE) between two stationary cationic orbitals (LUMO- β and HOMO- β), which together represents the initial hole density immediately following vertical ionization. We have also predicted that the strength of electron correlation has significant effect on the charge migration timescale in Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonded clusters. Vibration and rotation are also found to exhibit profound effect on attosecond charge migration dynamics through halogen bonds.

Graphical Abstract

The attosecond charge migration dynamics through Cl…..N, Cl…..O, Br…..N, and Br…..O halogen bonds depends on strength of electron correlation, donor and acceptor, the energy difference (ΔE) between two stationary cationic orbitals (LUMO-β and HOMO-β) involved in electronic superposition, vibration and rotation.

Keywords

Attosecond charge migration halogen bonds. 

Notes

Acknowledgment

This research was supported by the DST-SERB, India (SB/S1/PC-50/2013).

Supplementary material

12039_2016_1123_MOESM1_ESM.docx (2.4 mb)
(DOCX 2.40 MB)

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Copyright information

© Indian Academy of Sciences 2016

Authors and Affiliations

  • SANKHABRATA CHANDRA
    • 1
  • MOHAMMED MUSTHAFA IQBAL
    • 1
  • ATANU BHATTACHARYA
    • 1
    Email author
  1. 1.Department of Inorganic and Physical ChemistryIndian Institute of ScienceBangaloreIndia

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