Mechanism and control of molecular energy flow: A modeling perspective

Research output: Contribution to journalReview article

Abstract

Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N-6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical models of the molecule and control field.

Original languageEnglish (US)
Pages (from-to)53-63
Number of pages11
JournalTheoretical Chemistry Accounts
Volume109
Issue number2
DOIs
StatePublished - Mar 1 2003

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Chemical reactions
Hamiltonians
Molecules
chemical reactions
energy
Lasers
regularity
vibrational states
molecules
lasers

Keywords

  • Coherent control
  • Power law
  • Quantum diffusion
  • State space
  • Symplectic propagator

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Mechanism and control of molecular energy flow : A modeling perspective. / Gruebele, Martin.

In: Theoretical Chemistry Accounts, Vol. 109, No. 2, 01.03.2003, p. 53-63.

Research output: Contribution to journalReview article

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