Theoretical and Experimental Studies on Vibrational Energy Relaxation of the CO Stretching Mode of Acetone in Alcohol Solutions

Higashi, Masahiro; Hirai, Satori; Banno, Motohiro; Ohta, Kaoru; Saito, Shinji; Tominaga, Kazuhiro

doi:10.1021/jp310621p

Cited by 4 publications

(3 citation statements)

References 37 publications

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“…The shoulder GSB/SE experiences a much faster monoexponential decay which we attribute to faster vibrational relaxation facilitated by hydrogen bonding to the carbonyl group. The faster decay of the hydrogen bonded carbonyl is consistent with previous ultrafast mid-IR studies, which demonstrated that the vibrational lifetimes of carbonyl groups are sensitive to hydrogen bonding. − Specifically, hydrogen bonding to alcohol based donors accelerates vibrational energy relaxation of carbonyl groups. Considering the population decays in the context of previous experiments provides additional support for the assignment of the shoulder peak to the PhQ:1HB species.…”

Section: Resultssupporting

confidence: 87%

Resolving the Impact of Hydrogen Bonding on the Phylloquinone Cofactor through Two-Dimensional Infrared Spectroscopy

et al. 2022

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Two-dimensional infrared spectroscopy (2DIR) was applied to phylloquinone (PhQ), an important biological cofactor, to elucidate the impact of hydrogen bonding on the ultrafast dynamics and energetics of the carbonyl stretching modes. 2DIR measurements were performed on PhQ dissolved in hexanol, which served as the hydrogen bonding solvent, and hexane, which served as a non-hydrogen bonding control. Molecular dynamics simulations and quantum chemical calculations were performed to aid in spectral assignment and interpretation. From the position of the peaks in the 2DIR spectra, we extracted the transition frequencies for the fundamental, overtone, and combination bands of hydrogen bonded and non-hydrogen bonded carbonyl groups of PhQ in the 1635–1680 cm–1 region. We find that hydrogen bonding to a single carbonyl group acts to decouple the two carbonyl units of PhQ. Through analysis of the time-resolved 2DIR data, we find that hydrogen bonding leads to faster vibrational relaxation as well as an increase in the inhomogeneous broadening of the carbonyl groups. Overall, this work demonstrates how hydrogen bonding to the carbonyl groups of PhQ presents in the 2DIR spectra, laying the groundwork to use PhQ as a 2DIR probe to characterize the ultrafast fluctuations in the local environment of natural photosynthetic complexes.

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Section: Resultssupporting

confidence: 87%

Resolving the Impact of Hydrogen Bonding on the Phylloquinone Cofactor through Two-Dimensional Infrared Spectroscopy

et al. 2022

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“…A trajectory for 6 ns was carried out at each iteration step of the sequential sampling for the triethylamine and methanol solution systems. A longer trajectory with 12 ns was performed in each interaction step for 1-propanol solution because the hydrogen bond dynamics is slow . From these trajectories, 30,000 configurations were taken as the MM ensemble; i.e., the MM conformational samples were taken at every 300 fs for triethylamine and methanol and 600 fs for 1-propanol, respectively.…”

Section: Computational Detailsmentioning

confidence: 99%

“…A longer trajectory with 12 ns was performed in each interaction step for 1-propanol solution because the hydrogen bond dynamics is slow. 112 From these trajectories, 30,000 configurations were taken as the MM ensemble; i.e., the MM conformational samples were taken at every 300 fs for triethylamine and methanol and 600 fs for 1-propanol, respectively. The convergence criterion of the QM geometry optimization at each step of the sequential sampling was set to be 5.0 × 10 −4 hartrees/bohr for the largest component of the QM gradient.…”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical Study on Excited States of Bacteriochlorophyll a in Solutions with Density Functional Assessment

et al. 2014

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The excited-state properties of bacteriochlorophyll (BChl) a in triethylamine, 1-propanol, and methanol are investigated with the time-dependent density functional theory by using the quantum mechanical and molecular mechanical reweighting free energy self-consistant field method. It is found that no prevalent density functionals can reproduce the experimental excited-state properties, i.e., the absorption and reorganization energies, of BChl a in the solutions. The parameter μ in the range-separated hybrid functional is therefore optimized to reproduce the differences of the absorption energies in the solutions. We examine the origin of the differences of the absorption energies in the solutions and find that sensitive balance between contributions of structural changes and solute-solvent interactions determines the differences. The accurate description of the excitation with the density functional with the adjusted parameter is therefore essential to the understanding of the excited-state properties of BChl a in proteins and also the mechanism of the photosynthetic systems.

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Molecular Solution Behaviour of an Intermediate Biofuel Feedstock: Acetone–Butanol–Ethanol (ABE)

Zehentbauer

Kiefer

2015

ChemPhysChem

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Mixtures of acetone, butanol, and ethanol (ABE) are common intermediate products in the production of biofuels via biomass fermentation. Their separation to yield, for example, bio-butanol, is still difficult due to the lack of a fundamental understanding of these mixtures at the molecular level. In order to bridge this gap, a detailed analysis of characteristic features of the vibrational spectrum is carried out. A systematic study of the binary solutions of acetone with ethanol and butanol does not only reveal a universal behaviour at the molecular level when acetone is mixed with short-chain alcohols, it also shows that the phenomena at a length scale between the molecules and in the macroscopic solution need to be taken into account to understand the structure-property relationships. The size of self-associated molecule clusters seems to determine whether or not a system exhibits an azeotrope. When a second alcohol is added to an acetone/alcohol solution, no additional non-idealities are induced, which is advantageous for modelling ternary ABE mixtures and for improving their processing in the production of biofuels.

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Theoretical and Experimental Studies on Vibrational Energy Relaxation of the CO Stretching Mode of Acetone in Alcohol Solutions

Cited by 4 publications

References 37 publications

Resolving the Impact of Hydrogen Bonding on the Phylloquinone Cofactor through Two-Dimensional Infrared Spectroscopy

Resolving the Impact of Hydrogen Bonding on the Phylloquinone Cofactor through Two-Dimensional Infrared Spectroscopy

Theoretical Study on Excited States of Bacteriochlorophyll a in Solutions with Density Functional Assessment

Molecular Solution Behaviour of an Intermediate Biofuel Feedstock: Acetone–Butanol–Ethanol (ABE)

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