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Testing for memory-free spectroscopic coordinates by 3D IR exchange spectroscopy


Borek, Joanna A; Perakis, Fivos; Hamm, Peter (2014). Testing for memory-free spectroscopic coordinates by 3D IR exchange spectroscopy. Proceedings of the National Academy of Sciences of the United States of America, 111(29):10462-10467.

Abstract

Using 3D infrared (IR) exchange spectroscopy, the ultrafast hydrogen-bond forming and breaking (i.e., complexation) kinetics of phenol to benzene in a benzene/CCl4 mixture is investigated. By introducing a third time point at which the hydrogen-bonding state of phenol is measured (in comparison with 2D IR exchange spectroscopy), the spectroscopic method can serve as a critical test of whether the spectroscopic coordinate used to observe the exchange process is a memory-free, or Markovian, coordinate. For the system under investigation, the 3D IR results suggest that this is not the case. This conclusion is reconfirmed by accompanying molecular dynamics simulations, which furthermore reveal that the non-Markovian kinetics is caused by the heterogeneous structure of the mixed solvent.

Abstract

Using 3D infrared (IR) exchange spectroscopy, the ultrafast hydrogen-bond forming and breaking (i.e., complexation) kinetics of phenol to benzene in a benzene/CCl4 mixture is investigated. By introducing a third time point at which the hydrogen-bonding state of phenol is measured (in comparison with 2D IR exchange spectroscopy), the spectroscopic method can serve as a critical test of whether the spectroscopic coordinate used to observe the exchange process is a memory-free, or Markovian, coordinate. For the system under investigation, the 3D IR results suggest that this is not the case. This conclusion is reconfirmed by accompanying molecular dynamics simulations, which furthermore reveal that the non-Markovian kinetics is caused by the heterogeneous structure of the mixed solvent.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2014
Deposited On:09 Oct 2014 09:04
Last Modified:05 Aug 2017 09:20
Publisher:National Academy of Sciences
ISSN:0027-8424
Funders:Swiss National Science Foundation (SNF) through the National Center of Competence and Research (NCCR) MUST
Free access at:PubMed ID. An embargo period may apply.
Publisher DOI:https://doi.org/10.1073/pnas.1406967111
PubMed ID:25002483

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