Spectroscopic studies of hydrogen bonding in H2S

Lowder, J.E.; Kennedy, Lyndon; Sulzmann, K.G.P.; Penner, S.S.

doi:10.1016/0022-4073(70)90126-3

Cited by 43 publications

(12 citation statements)

References 3 publications

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“…third d function and an extra sand p; a second p on hydrogen from Martin was also tried, but did not greatly improve a(O). The counterpoised (CP) and uncounterpoised (UCP) dimerization energies for the three larger basis sets, at the minimum energy configuration, are presented in Table III and may be contrasted with the experimental minimum of Lowder et al 16 of -0.074 ± 0.013 eV. Our minimum geometry is in agreement with Kerns and Allen.…”

Section: Basis Setsupporting

confidence: 79%

Ab initio potentials for (H2S)2, including studies of effects from third-order many-body perturbation theory and three-body nonadditivity

Beck

1990

The Journal of Chemical Physics

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Articles you may be interested inErratum: A b i n i t i o potentials for (H2S)2, including studies of effects from thirdorder manybody perturbation theory and threebody nonadditivity [J. Chem. Phys. 9 2, 3605 (1990)] J. Chem. Phys. 92, 6338 (1990); 10.1063/1.458610 Multipole moments, polarizabilities, and hyperpolarizabilities for N2 from fourthorder manybody perturbation theory calculations J. Chem. Phys. 88, 7623 (1988); 10.1063/1.454327Convergence studies of the effective valence shell Hamiltonian for correlation energies of the fluorine atom and its ions using third order quasidegenerate manybody perturbation theory Analysis of a b i n i t i o effective valence shell Hamiltonian calculations using third order quasidegenerate manybody perturbation theory Ab initio Hartree-Fock (HF) and many-body perturbation theory through second (E2) and third order (E3) were used to generate pair potentials for (H 2 S) 2' Several basis sets were developed by optimizing polarization functions with the zeroth-order dipole or quadrupole polarizabilities. Approximately 30 ab initio points (fully counterpoised HF + E2) in each of two larger basis sets were fit with site-site potentials. Intermediate potentials for fewer points indicate that only about 30 points are a sufficient data base to predict energies in the vicinity of the well with an accuracy of about 10%. The best ab initio well depth produced ( -0.0693 eV) lies at 94% of the only published experimental value ( -0.074 ± 0.013 eV), although arguments are presented which indicate that the true (H 2 Sh minimum may lie below -0.08 eV. The role ofE3 and nonadditive effects has also been explored, but they were found not to account for the major part of the remaining discrepancy between our best number and experiment.

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Section: Basis Setsupporting

confidence: 79%

Ab initio potentials for (H2S)2, including studies of effects from third-order many-body perturbation theory and three-body nonadditivity

Beck

1990

The Journal of Chemical Physics

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“…Its hydrogen-bond energies are calculated to be -1.9 kcal/mol (4-3 1G) and -1.7 (4-3 lG(*)). These compare favorably to -1.7 + 0.3 by an infrared intensity measurement (8). As the cluster size becomes larger, therefore, the positive charge is dispersed and the overestimate of 4-31G gets smaller.…”

Section: Resultssupporting

confidence: 61%

A theoretical study on the structures and stabilities of protonated hydrogen sulphide – hydrogen sulfide clusters

Yamabe¹,

Minato²,

Sakamoto³

et al. 1985

Can. J. Chem.

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SHINICHI YAMABE, TSUTOMU MINATO, MAKINO SAKAMOTO, and KIMIHIKO HIRAO. Can. J. Chem. 63, 2571 (1985). An ab initio MO calculation is made on the H3S+(H2S), cluster ( n = 0-5). For n = 1 , full thermodynamic data are reproduced theoretically, and for n = 1, 2, and 3 the effect of d functions on the structure and energies is investigated. On the basis of the present results, the accuracy of two conflicting experimental data is examined.SHlNICHl YAMABE, TsuTOMU MINATO, MAKINO SAKAMOTO et KIMIHIKO HIRAO. Can.

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“…We turn now to what we shall term our 'loose' or 'baggy' fits of Equation (5). As detailed in Table 1, we note that observed 8's are closely reproduced for a broad range of n-and K values, e.g.…”

Section: Treatment Of Thiol Hydrogen Bonding Datamentioning

confidence: 93%

“…Except for the figures for HzS, which were taken from Ref 5. and have the reference state of 1 atm gas phase, the data have the indicated mole/l.…”

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confidence: 99%

Self‐association of thiols. The baggy fit problem in weak complexes

Miller

1973

Org. Magn. Reson.

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Abstract-The PMR technique has been used to obtain thermodynamic data for hydrogen bonding of alkanethiols (RSH) in 1:l dimers in carbon tetrachloride. At ca. 303°K these are (R, C,HI1, 1.3 2, 0.7 & 0.3, 15 f 1. Alkanethiol self-association is weak, and although an exact expression [Eqn. (5)] reproduces spectral data precisely, the fit is sufficiently 'loose' or 'baggy' so that values of K, AH" and AS' are uncertain. The methodology of the treatment of self-association data and their errors is examined and Deranleau's useful approach is extended. The impossibility of obtaining reliable data for very weak (< 10 %) or very strong (>90 %) associations by techniques equivalent to ours is emphasized. The possibility of cyclic thiol dimers is discussed. It is suggested that the PMR method cannot give trustworthy selfassociation data for aryl or arylalkylthiols because of the relatively large anisotropy effects introduced into the dilution shift.IO4KDESPITE its importance, little is known about the quantitative aspects of hydrogen bonding at a sulfur site. Certainly, many qualitative observations and a few equilibrium constants ( K ) have been r e c~r d e d ,~.~, * but there is only one complete set of thermodynamic data, i.e. for hydrogen ~ulfide.~ Although infrared (IR) techniques have been applied to this problem, the extraction of K values from the observations appears to be difficult or ~n c e r t a i n .~,~ to * Proton magnetic resonance (PMR) spectroscopy, which is the approach we used, is not without its p r o b l e m~.~~~J~J l Nevertheless, we obtained complete thermodynamic data, viz. K , AH" and AS', for the self-association of five alkanethiols in carbon tetrachloride. 2RSW + (RSH),(1) In recent years, there has been increased concern over the theory and methodology of studying association phenomena.ll to l4 Advances, especially computer processing of data, have rendered some older measurements, controversies, experimental strategies, etc., irrelevant or obsolete. Perhaps even more important to this work is the suggestion that conventionally obtained 'association' constants of weak complexes by nonthermodynamic measurements probably include 'sociation' constants, which involve those 'complexes' over and above those one would estimate from probabilities for a random mixture.12 For this reason, we cannot rely on most of the previously published equilibrium data for selfassociation of t h i o l~.~,~,~J~ In fact , our present analysis provides a good example of the vulnerable state of the art in the area of weak hydrogen bonding, as studied by PMR. EXPERIMENTALThiols were carefully distilled and the middle cuts were stored over Linde 4A molecular sieves; checks by VPC and IR and PMR spectroscopy established their purities (>99.5 %).' The solvent was Eastman Spectrograde carbon tetrachloride. SolutionsAll flasks and NMR tubes were intensively dried and flushed with prepurified nitrogen before use. The thiols were weighed in volumetric flasks and made up to volume at 25" with carbon tetrachloride containing -1 % t...

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Spectroscopic studies of hydrogen bonding in H2S

Cited by 43 publications

References 3 publications

Ab initio potentials for (H2S)2, including studies of effects from third-order many-body perturbation theory and three-body nonadditivity

Ab initio potentials for (H2S)2, including studies of effects from third-order many-body perturbation theory and three-body nonadditivity

A theoretical study on the structures and stabilities of protonated hydrogen sulphide – hydrogen sulfide clusters

Self‐association of thiols. The baggy fit problem in weak complexes

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