Quantitative infrared-spectroscopic investigations of hydrogen-bond cooperativity

Kleeberg, H.; Klein, Dietmar; Luck, W. A. P.

doi:10.1021/j100296a019

Cited by 180 publications

(72 citation statements)

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“…This cooperative effect of hydrogen bond has been also studied by others. 52,53 This can be confirmed by both the binding energies of hydrogen bonds listed in Table 1 and the calculated vibrational absorption spectra in the ground state, as Table 1. Primary bond length in optimized structures of isolated FOH and hydrogen-bonded complexes in different electronic states, as well as their binding energies of hydrogen bond.…”

Section: à42supporting

confidence: 64%

Facilitated Photolysis of 9-Fluorenol in Alcohols by Excited-State Hydrogen Bond Reorganization

Liu

Zhou

2012

J. Theor. Comput. Chem.

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Time-dependent density functional theory (TDDFT) and second-order coupled cluster method with resolution-of-the-identity approximation (RICC2) were used to investigate the photolysis dynamics of 9-fluorenol (FOH) in alcohols. In this work, a novel mechanism for the accelerated photolysis dynamics of FOH in alcohols is proposed for the first time. The two hydrogen bonds present different effects in the dissociation process of C 9 ÀO bond in MeOH Á Á Á FOH Á Á Á MeOH trimer: formation of hydrogen bond MeOH Á Á Á FOH could weaken the C 9 ÀO bond, while, hydrogen bond FOH Á Á Á MeOH fastens the bond. Moreover, the thermodynamic equilibrium can be accomplished in both ground and excited states between hydrogen-bonded complexes, since the hydrogen bond reorganization occurs in hundreds of femtosecond upon the excitation. The excited-state potential energy (PE) curves along C 9 ÀO bond have been optimized in S 1 state. The cleavage of C 9 ÀO bond upon the photoexcitation would be facilitated effectively in MeOH Á Á Á FOH dimer. This leads the thermodynamic equilibrium between hydrogen-bonded complexes leaning to the side of MeOH Á Á Á FOH dimer to quench the fluorescence. Therefore, the photolysis of 9-fluorenol in alcohols can be facilitated effectively by MeOH Á Á Á FOH hydrogen bond via excited-state hydrogen bond reorganization. Additionally, the excited-state hydrogen bond reorganization is also the rate-controlling step in photolysis of FOH in alcohols, since there is no barrier in the PE curve of MeOH Á Á Á FOH dimer.

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Section: à42supporting

confidence: 64%

Facilitated Photolysis of 9-Fluorenol in Alcohols by Excited-State Hydrogen Bond Reorganization

Liu

Zhou

2012

J. Theor. Comput. Chem.

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“…Because of the cooperativity of hydrogen bonding, 32 the intermolecular bonds are strengthened as the number of incorporated molecules increases. In fact, a decrease of 70-90 cm -1 can be observed in the peak center between the beginning of the aggregation process in CCl 4 and the liquid state.…”

Section: Resultsmentioning

confidence: 99%

Molecular Structure of Butanediol Isomers in Gas and Liquid States: Combination of DFT Calculations and Infrared Spectroscopy Studies

et al. 2003

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Density functional theory (Becke3LYP/6-311++G**) conformational analysis was carried out for all positional butanediol isomers. Taking into account the relative populations of the most stable conformers at 298.15 K, the weighted mean enthalpies of each butanediol isomer in the gas state were computed. Combining these results with the experimental values for the enthalpies of vaporization at 298.15 K, an estimate of the enthalpy of each of the butanediol isomers in the liquid state was obtained and discussed. The insight into the structural changes at the molecular level from the isolated molecule to the condensed state was improved by an infrared spectroscopy study in the OH stretching region, which was carried out for a wide range of concentrations of carbon tetrachloride solutions and pure liquids. The spectroscopic studies essentially confirmed the results derived from the combination of the computational and calorimetric studies.

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“…where u ij (1,2) is the association energy and g ij (1,2) is the pair distribution function between the associating group in reference system (i.e., when the association is switched off).…”

Section: Figmentioning

confidence: 99%

“…Infrared spectroscopy thus represents the most popular experimental methods to study the microscopic structure of the hydrogen bonded systems. [2][3][4][5][6][7][8] The neutron-or x-ray diffraction techniques [9][10][11][12][13] and the dielectric relaxation 14,15 can provide further information about the structure and dynamics of the hydrogen bonded systems. Indirect information about the hydrogen bonding can be deduced also from macroscopic properties (e.g., from the viscosity measurements or PvT behaviour and phase equilibrium data).…”

Section: Introductionmentioning

confidence: 99%

Size distribution of associated clusters in liquid alcohols: Interpretation of simulation results in the frame of SAFT approach

Janeček

Paricaud

2013

The Journal of Chemical Physics

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The size distribution and topology of associated clusters for primary alcohols is studied using molecular dynamics simulations. Liquid ethanol, propanol, butanol, hexanol, and octanol are simulated at pressure P = 1 bar and temperatures T = 300 K, T = 350 K, and T = 400 K. The fractions of molecules with different sets of hydrogen bonded partners, the size of associated cluster and the site-site distribution functions between atoms participating on hydrogen bonding are extracted from simulated trajectories. For all alcohols longer than ethanol, the length of the alkyl chain has only a marginal effect on the association. Consequently, related properties like coordination numbers of hydroxyl group, size distribution of associates, or fractions of differently coordinated alcohol molecules are independent on the molecular size. Although we employed a force-field without involved polarizability, we observe a positive cooperativity of hydrogen bonding simply as a consequence of steric and electrostatic interactions. The size and topology of associates is analyzed within the frame of 3B model of statistical association fluid theory. Although this approach enables good thermodynamic description of systems containing associating compounds, several insufficiencies appear in the description at molecular level. © 2013 AIP Publishing LLC.[http://dx.doi.org/10.1063/1.4827107]

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Quantitative infrared-spectroscopic investigations of hydrogen-bond cooperativity

Cited by 180 publications

References 0 publications

Facilitated Photolysis of 9-Fluorenol in Alcohols by Excited-State Hydrogen Bond Reorganization

Facilitated Photolysis of 9-Fluorenol in Alcohols by Excited-State Hydrogen Bond Reorganization

Molecular Structure of Butanediol Isomers in Gas and Liquid States: Combination of DFT Calculations and Infrared Spectroscopy Studies

Size distribution of associated clusters in liquid alcohols: Interpretation of simulation results in the frame of SAFT approach

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