Spectroscopy and dynamics of double proton transfer in formic acid dimer
| Autor: | Zeina Maroun, Markus Meuwly, Henrik G. Kjaergaard, Kasper Mackeprang, Zhen-Hao Xu |
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| Rok vydání: | 2016 |
| Předmět: |
010304 chemical physics
Chemistry Formic acid Dimer General Physics and Astronomy Infrared spectroscopy 010402 general chemistry 01 natural sciences Potential energy Spectral line 0104 chemical sciences chemistry.chemical_compound Molecular dynamics Deuterium Computational chemistry 0103 physical sciences Physical chemistry Physical and Theoretical Chemistry Spectroscopy |
| Zdroj: | Mackeprang, K, Xu, Z-H, Maroun, Z, Meuwly, M & Kjærgaard, H G 2016, ' Spectroscopy and dynamics of double proton transfer in formic acid dimer ', Physical Chemistry Chemical Physics, vol. 18, no. 35, pp. 24654-24662 . https://doi.org/10.1039/c6cp03462d |
| DOI: | 10.5451/unibas-ep53179 |
| Popis: | We present the isolated gas phase infrared spectra of formic acid dimer, (HCOOH)2, and its deuterated counterpart formic-d acid, (DCOOH)2, at room temperature. The formic acid dimer spectrum was obtained by spectral subtraction of a spectrum of formic acid vapor recorded at low pressure from that recorded at a higher pressure. The spectra of formic acid vapor contain features from both formic acid monomer and formic acid dimer, but at low and high pressures of formic acid, the equilibrium is pushed towards the monomer and dimer, respectively. A similar approach was used for the formic-d acid dimer. Building on the previous development of the Molecular Mechanics with Proton Transfer (MMPT) force field for simulating proton transfer reactions, molecular dynamics (MD) simulations were carried out to interpret the experimental spectra in the OH-stretching region. Within the framework of MMPT, a combination of symmetric single and double minimum potential energy surfaces (PESs) provides a good description of the double proton transfer PES. In a next step, potential morphing together with electronic structure calculations at the B3LYP and MP2 level of theory was used to align the computed and experimentally observed spectral features in the OH-stretching region. From this analysis, a barrier for double proton transfer between 5 and 7 kcal mol-1 was derived, which compares with a CCSD(T)/aug-cc-pVTZ calculated barrier of 7.9 kcal mol-1. Such a combination of experimental and computational techniques for estimating barriers for proton transfer in gas phase systems is generic and holds promise for further improved PESs and energetics of these important systems. Additional MD simulations at the semi-empirical DFTB level of theory agree quite well for the center band position but underestimate the width of the OH-stretching band. |
| Databáze: | OpenAIRE |
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