FTIR Spectrum of the ν4Band of DCOOD

Tan, T.L.; Goh, Khim Yong; Ong, P.P.; Teo, Hock-Hai

doi:10.1006/jmsp.1999.7821

Cited by 14 publications

(2 citation statements)

References 6 publications

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“… a The m values are the slopes determined in intensity–intensity correlation plots. b Reference . c Reference . d Reference . e Reference . f Reference . g Reference . h Reference . i Reference . j Reference . k Reference . l Reference . …”

Section: Experimental and Resultsmentioning

confidence: 99%

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen II: Deuterated Reaction Studies

Wonderly

Anderson

2014

J. Phys. Chem. A

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It is difficult to determine whether the measured rate constant for reaction of atomic hydrogen with formic acid reported in Part 1 reflects the H atom quantum diffusion rate or the rate constant for the tunneling reaction step. In Part 2 of this series, we present kinetic studies of the postphotolysis H atom reactions with deuterated formic acid (DCOOD) to address this ambiguity. Short duration 193 nm in situ photolysis of DCOOD trapped in solid parahydrogen results in partial depletion of the DCOOD precursor and photoproduction of primarily CO, CO2, DOCO, HCO and mobile H atoms. At 1.9 K we observe post-irradiation growth in the concentrations of DOCO and HCO that can be explained by H atom tunneling reactions with DCOOD and CO, respectively. Conducting experiments with different deuterium isotopomers of formic acid (DCOOD, DCOOH, HCOOD and HCOOH) provides strong circumstantial evidence the reaction involves H atom abstraction from the alkyl group of formic acid. Further, the anomalous temperature dependence measured for the H + HCOOH reaction in Part 1 is also observed for the analogous reactions with deuterated formic acid. The rate constants extracted for H atom reactions with DCOOD and HCOOH are equivalent to within experimental uncertainty. This lack of a kinetic isotope effect in the measured rate constant is interpreted as evidence the reactions are diffusion limited; the measured rate constant reflects the H atom diffusion rate and not the tunneling reaction rate. Whether or not H atom reactions with chemical species in solid parahydrogen are diffusion limited is one of the outstanding questions in this field, and this work makes significant strides toward showing the reaction kinetics with formic acid are diffusion limited.

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Section: Experimental and Resultsmentioning

confidence: 99%

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen II: Deuterated Reaction Studies

Wonderly

Anderson

2014

J. Phys. Chem. A

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“…All experimental fundamental band centers of trans-DCOOD measured in the gas phase have been reported, [51][52][53][54][55][56][57] and the most recent results are provided in Table II. Experimental analysis including rotation has been completed for the ν 1 and ν 4 fundamentals, 55,56 i.e., the OD and C-O stretches, respectively. Two high-energy overtone and combination bands were also reported.…”

Section: A Trans-dcoodmentioning

confidence: 99%

Vibrational states of deuterated trans- and cis-formic acid: DCOOH, HCOOD, and DCOOD

Aerts

Carbonnière

Richter

et al. 2020

The Journal of Chemical Physics

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The vibrational eigenenergies of the deuterated forms of formic acid (DCOOD, HCOOD, and DCOOH) have been computed using the block-improved relaxation method as implemented in the Heidelberg multi-configuration time-dependent Hartree package on a previously published potential energy surface [J. Chem. Phys. 148, 064303 (2018)] generated at the CCSD(T)-F12a/aug-cc-pVTZ-F12 level of theory. Fundamental, combination band, and overtone transition frequencies of the trans isomer were computed up to ∼ 3000 cm-1 with respect to the zero point energy and assignments were determined by visualisation of the reduced densities. Root mean square deviation of computed fundamental transition frequencies with experimentally available gas-phase measurements are 8, 7, and 3 cm-1 for trans-DCOOD, HCOOD, and DCOOH, respectively. The fundamental transition frequencies are provided for the cis isomer of all deuterated forms; experimental measurements of these frequencies for the deuterated cis isotopologues are not yet available and the present work may guide their identification.

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Rovibrational Constants for the ν6 and 2ν9 Bands of HCOOD by Fourier Transform Infrared Spectroscopy

Tan

Goh

Ong

et al. 1999

Journal of Molecular Spectroscopy

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FTIR Spectrum of the ν4Band of DCOOD

Cited by 14 publications

References 6 publications

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen II: Deuterated Reaction Studies

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen II: Deuterated Reaction Studies

Vibrational states of deuterated trans- and cis-formic acid: DCOOH, HCOOD, and DCOOD

Rovibrational Constants for the ν6 and 2ν9 Bands of HCOOD by Fourier Transform Infrared Spectroscopy

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