Analysis of state-specific vibrations coupled to the unidirectional energy transfer in conjugated dendrimers

J Phys Chem A. 2012 Oct 11;116(40):9802-10. doi: 10.1021/jp301293e. Epub 2012 Oct 2.

Abstract

The nonadiabatic excited-state molecular dynamics (NA-ESMD) method and excited-state instantaneous normal modes (ES-INMs) analyses have been applied to describe the state-specific vibrations that participate in the unidirectional energy transfer between the coupled chromophores in a branched dendrimeric molecule. Our molecule is composed of two-, three-, and four-ring linear poly(phenyleneethynylene) (PPE) units linked through meta-substitutions. After an initial laser excitation, an ultrafast sequential S(3) → S(2) → S(1) electronic energy transfer from the shortest to longest segment takes place. During each S(n) → S(n-1) (n = 3, 2) transition, ES-INM(S(n)) and ES-INM(S(n-1)) analyses have been performed on S(n) and S(n-1) states, respectively. Our results reveal a unique vibrational mode localized on the S(n) state that significantly matches with the corresponding nonadiabatic coupling vector d(n,(n-1)). This mode also corresponds to the highest frequency ES-INM(S(n)) and it is seen mainly during the electronic transitions. Furthermore, its absence as a unique ES-INM(S(n-1)) reveals that state-specific vibrations play the main role in the efficiency of the unidirectional S(n) → S(n-1) electronic and vibrational energy funneling in light-harvesting dendrimers.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Dendrimers / chemistry*
  • Energy Transfer
  • Molecular Dynamics Simulation*
  • Polymers / chemistry*
  • Vibration*

Substances

  • Dendrimers
  • Polymers
  • poly(phenylene ethynylene)