Abstract
Hydrogen-bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen-bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other nonmigration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems.
| Original language | English |
|---|---|
| Pages (from-to) | 2383-2389 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry B |
| Volume | 114 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - 2010 Feb 25 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Surfaces, Coatings and Films
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
Hydrogen bond migration between molecular sites observed with ultrafast 2D IR chemical exchange spectroscopy. / Rosenfeld, Daniel E.; Kwak, Kyungwon; Gengeliczki, Zsolt; Fayer, M. D.
In: Journal of Physical Chemistry B, Vol. 114, No. 7, 25.02.2010, p. 2383-2389.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Hydrogen bond migration between molecular sites observed with ultrafast 2D IR chemical exchange spectroscopy
AU - Rosenfeld, Daniel E.
AU - Kwak, Kyungwon
AU - Gengeliczki, Zsolt
AU - Fayer, M. D.
PY - 2010/2/25
Y1 - 2010/2/25
N2 - Hydrogen-bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen-bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other nonmigration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems.
AB - Hydrogen-bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen-bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other nonmigration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems.
UR - http://www.scopus.com/inward/record.url?scp=77249131993&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77249131993&partnerID=8YFLogxK
U2 - 10.1021/jp911452z
DO - 10.1021/jp911452z
M3 - Article
C2 - 20121275
AN - SCOPUS:77249131993
VL - 114
SP - 2383
EP - 2389
JO - Journal of Physical Chemistry B Materials
JF - Journal of Physical Chemistry B Materials
SN - 1520-6106
IS - 7
ER -