The most stable conformer of benzyl alcohol

Miller, Benjamin J.; Kjaergaard, Henrik G.; Hattori, Kaori; Ishiuchi, Shun‐ichi; Fujii, Masaaki

doi:10.1016/j.cplett.2008.10.028

Cited by 22 publications

(26 citation statements)

References 38 publications

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“…The −OH moiety can either point away from the aromatic ring (out), or toward the aromatic ring (in). Conformers with the OH group in the ring plane, as reported by Miller et al for benzyl alcohol with the B3LYP functional, 87 were found to be transition states for veratrole alcohol with the B2PLYPD method. Throughout a full internal rotation of the −CH 2 OH group, four minima are visited, each of which exhibits stable in/out conformers.…”

Section: ■ Results and Discussionmentioning

confidence: 78%

Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

et al. 2014

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To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

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Section: ■ Results and Discussionmentioning

confidence: 78%

Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

et al. 2014

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“…It is assumed that this peak contains only MGD (although it may also contain a small tetrol contribution) and this feature was integrated to obtain an integrated absorbance. The integrated absorbance along with the theoretically determined cross-section, σ OH , of 9.14 × 10 −18 cm molecule −1 , which is in agreement with a typical alcohol cross-section (34,38,39), was used in Eq. 1 to determine MGD N∕v.…”

Section: Resultsmentioning

confidence: 89%

Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

Axson

Takahashi

Haan

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

106

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In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, K P , for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry.hydration | equilibrium constant | water clusters

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“…The errors of the values are given in parentheses non-aromatic alcohols. 50 So far, it seems to have been applied predominantly to aromatic monomers, 51 but not to non-aromatic alcohol dimers. An advantage is that the high sensitivity makes higher overtones easily accessible, whereas the present technique is currently limited to second overtones of monomers.…”

Section: Ethanolmentioning

confidence: 99%

Alcohol dimers – how much diagonal OH anharmonicity?

Kollipost

Papendorf

Lee

et al. 2014

Phys. Chem. Chem. Phys.

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The OH bond of methanol, ethanol and t-butyl alcohol becomes more anharmonic upon hydrogen bonding and the infrared intensity ratio between the overtone and the fundamental transition of the bridging OH stretching mode decreases drastically. FTIR spectroscopy of supersonic slit jet expansions allows to quantify these effects for isolated alcohol dimers, enabling a direct comparison to anharmonic vibrational predictions. The diagonal anharmonicity increase amounts to 15-18%, growing with increasing alkyl substitution. The overtone/fundamental IR intensity ratio, which is on the order of 0.1 or more for isolated alcohols, drops to 0.004-0.001 in the hydrogen-bonded OH group, making overtone detection very challenging. Again, alkyl substitution enhances the intensity suppression. Vibrational second order perturbation theory appears to capture these effects in a semiquantitative way. Harmonic quantum chemistry predictions for the hydrogen bond-induced OH stretching frequency shift (the widely used infrared signature of hydrogen bonding) are insufficient, and diagonal anharmonicity corrections from experiment make the agreement between theory and experiment worse. Inclusion of anharmonic cross terms between hydrogen bond modes and the OH stretching mode is thus essential, as is a high level electronic structure theory. The isolated molecule results are compared to matrix isolation data, complementing earlier studies in N2 and Ar by the more weakly interacting Ne and p-H2 matrices. Matrix effects on the hydrogen bond donor vibration are quantified.

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The most stable conformer of benzyl alcohol

Cited by 22 publications

References 38 publications

Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

Alcohol dimers – how much diagonal OH anharmonicity?

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