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VIBRATIONAL DYNAMICS OF TRIFLUOROACETIC ACID AND FORMIC ACID IN GAS AND DILUTE SOLUTION: CRACKING OPEN GAS PHASE ACID DIMERS

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/30478

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Title: VIBRATIONAL DYNAMICS OF TRIFLUOROACETIC ACID AND FORMIC ACID IN GAS AND DILUTE SOLUTION: CRACKING OPEN GAS PHASE ACID DIMERS
Creators: Crum, Pam L.; Dian, Brian C.; Yoo, Hyun S.; Hinkle, Charlotte E.; Pate, Brooks H.
Issue Date: 2005
Abstract: Ultrafast time-domain transient absorption spectroscopy is used to study the vibrational dynamics of the cyclic hydrogen bonded dimers of trifluoroacetic acid and formic acid in both the gas- and solution-phase. Deposition of energy into the broad dimer bands of these acid dimers in the gas-phase provides the means to break open the dimer, as evidenced by the growth of a \`{ }\`{ }free O-H\'{ }\'{ } absorbance at \ { }3580\wn on the time scales of energy flow out of the initially excited dimer region. In trifluoroacetic acid there is no change in the rate of \`{ }\`{ }free O-H\'{ }\'{ } growth with varying pump frequency between 2596\wn and 3131\wn. Spectrally resolved pump-probe experiments are performed to reveal the evolution of a broad range of the spectra in time, which facilitates interpretation of the dynamics behind the time scales provided by single frequency measurements. When the acid dimers are solvated (0.05M CCl$_4$ solution), energy pumped into the broad dimer band can be cooled out by the solvent, making it unavailable to the process of dimer opening.
URI: http://hdl.handle.net/1811/30478
Other Identifiers: 2005-RI-06
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