Dynamics of Proton Transfer and Vibrational Relaxation in Dilute Hydrofluoric Acid

• 城塚, 達也

• 安藤, 耕司

抄録

The molecular mechanisms in both vibrational relaxation and proton transfer (PT) associated with infrared (IR)-induced PT in a dilute hydrofluoric acid solution at ambient temperature are studied by molecular dynamics (MD) simulations with the multistate empirical valence bond model. To investigate the solvation dynamics, a collective solvent coordinate and its perpendicular bath modes are defined from the diabatic energy gap and their motions are examined by the generalized Langevin equation (GLE) formalism. The GLE analysis using the equilibrium MD simulation shows that the major solvent reorganizations in the PT are represented by the libration and hindered translation. In particular, the libration gives the stronger coupling to the solvent reorganization and the faster relaxation. The nonequilibrium MD simulation demonstrated that both the HF stretching vibration and the solvent reorganization relax on a similar time scale and thus compete in the PT. It also supported the “presolvation mechanism” for the PT in this system.

収録刊行物

• The Journal of Physical Chemistry A

  The Journal of Physical Chemistry A 115 (5), 678-684, 2011-01-06

  American Chemical Society (ACS)

キーワード

• Physical and Theoretical Chemistry

詳細情報

• CRID: 1050282810815065728
• NII論文ID: 120005853259
• ISSN: 10895639
• ISSN: 15205215
• HANDLE: 2433/217073
• 本文言語コード: en
• 資料種別: journal article
• データソース種別:
  • IRDB
  • CiNii Articles