Effect of ring substitution on the S-H bond dissociation enthalpies of thiophenols. An experimental and computational study

There are conflicting reports on the origin of the effect of Y substituents on the S-H bond dissociation enthalpies (BDEs) in 4-Y-substituted thiophenols, 4-YC(6)H(4)S-H. The differences in S-H BDEs, [4-YC(6)H(4)S-H] - [C(6)H(5)S-H], are known as the total (de)stabilization enthalpies, TSEs, where TSE = RSE - MSE, i.e., the radical (de)stabilization enthalpy minus the molecule (de)stabilization enthalpy. The effects of 4-Y substituents on the S-H BDEs in thiophenols and on the S-C BDEs in phenyl thioethers are expected to be almost identical. Some S-C TSEs were therefore derived from the rates of homolyses of a few 4-Y-substituted phenyl benzyl sulfides, 4-YC(6)H(4)S-CH(2)C(6)H(5), in the hydrogen donor solvent 9,10-dihydroanthracene. These TSEs were found to be -3.6 +/- 0.5 (Y = NH(2)), -1.8 +/- 0.5 (CH(3)O), 0 (H), and 0.7 +/- 0.5 (CN) kcal mol(-1). The MSEs of 4-YC(6)H(4)SCH(2)C(6)H(5) have also been derived from the results of combustion calorimetry, Calvet-drop calorimetry, and computational chemistry (B3LYP/6-311+G(d,p)). The MSEs of these thioethers were -0.6 +/- 1.1 (NH(2)), -0.4 +/- 1.1 (CH(3)O), 0 (H), -0.3 +/- 1.3 (CN), and -0.8 +/- 1.5 (COCH(3)) kcal mol(-1). Although all the enthalpic data are rather small, it is concluded that the TSEs in 4-YC(6)H(4)SH are largely governed by the RSEs, a somewhat surprising conclusion in view of the experimental fact that the unpaired electron in C(6)H(5)S(*) is mainly localized on the S. The TSEs, RSEs, and MSEs have also been computed for a much larger series of 4-YC(6)H(4)SH and 4-YC(6)H(4)SCH(3) compounds by using a B3P86 methology and have further confirmed that the S-H/S-CH(3) TSEs are dominated by the RSEs. Good linear correlations were obtained for TSE = rho(+)sigma(p)(+)(Y), with rho(+) (kcal mol(-1)) = 3.5 (S-H) and 3.9 (S-CH(3)). It is also concluded that the SH substituent is a rather strong electron donor with a sigma(p)(+)(SH) of -0.60, and that the literature value of -0.03 is in error. In addition, the SH rotational barriers in 4-YC(6)H(4)SH have been computed and it has been found that for strong electron donating (ED) Ys, such as NH(2), the lowest energy conformer has the S-H bond oriented perpendicular to the aromatic ring plane. In this orientation the SH becomes an electron withdrawing (EW) group. Thus, although the OH group in phenols is always in-plane and ED irrespective of the nature of the 4-Y substituent, in thiophenols the SH switches from being an ED group with EW and weak ED 4-Ys, to being an EW group for strong ED 4-Ys.     

Nonthermal melting of a charge density wave in TiSe2

We use time-resolved optical reflectivity and x-ray diffraction with femtosecond resolution to study the dynamics of the structural order parameter of the charge density wave phase in TiSe2. We find that the energy density required to melt the charge density wave nonthermally is substantially lower than that required for thermal suppression and is comparable to the charge density wave condensation energy. This observation, together with the fact that the structural dynamics take place on an extremely fast time scale, supports the exciton condensation mechanism for the charge density wave in TiSe2.     

Transport through cavities with tunnel barriers: a semiclassical analysis

We study the influence of a tunnel barrier on the quantum transport through a circular cavity. Our analysis in terms of classical trajectories shows that the semiclassical approaches developed for ballistic transport can be adapted to deal with the case where tunneling is present. Peaks in the Fourier transform of the energy-dependent transmission and reflection spectra exhibit a nonmonotonic behaviour as a function of the barrier height in the quantum mechanical numerical calculations. Semiclassical analysis provides a simple qualitative explanation of this behaviour, as well as a quantitative agreement with the exact calculations. The experimental relevance of the classical trajectories in mesoscopic and microwave systems is discussed. Received: 23 October 1997 / Received in final form and Accepted: 11 March 1998     

Spatiotemporal stability of a femtosecond hard-x-ray undulator source studied by control of coherent optical phonons

We report on the temporal and spatial stability of the first tunable femtosecond undulator hard-x-ray source for ultrafast diffraction and absorption experiments. The 2.5-1 Angstrom output radiation is driven by an initial 50 fs laser pulse employing the laser-electron slicing technique. By using x-ray diffraction to probe laser-induced coherent optical phonons in bulk bismuth, we estimate an x-ray pulse duration of 140+/-30 fs FWHM with timing drifts below 30 fs rms measured over 5 days. Optical control of coherent lattice motion is demonstrated.     

High impact shock testing of fiber-optic components

MIL-S-901 High Impact Shock tests were performed on commercial-grade and ruggedized fiber-optic connectors, splices, and switches. Both single-mode and multimode connectors and splices were tested. Only multimode switches were tested. Transient losses of varying magnitudes and durations were observed. Most components suffered no permanent degradation.     

Isomerisation of decatetraenes and dimethyldecatetraenes via pentadienyl and 3-methylpentadienyl radicals

The thermal isomerisations of E,E-deca-l,3,7,9-tetraene and E,E-3,7-dimethyldeca-l,3,7,9-tetraene take place via the intermediacy of pentadienyl and 3-methylpentadienyl radicals, respectively, rather than by concerted Cope type rearrangements. The pentadienyl radicals isomerise to pairs of E- and Z-pentadienyl radicals which recombine by end to end and end to centre, but not centre to centre, coupling to give mixtures of isomeric decatetraenes. The relative free energies of formation of these decatetraenes were derived from their equilibrium proportions and compared with relative enthalpies of formation calculated by the empirical MM2(87) method and the semiempirical AM1 and PM3 SCF MO methods. None of these theories was successful at predicting and rationalizing the experimentally observed enthalpy changes. However, they all were somewhat better in dealing with branching than with cis/trans isomerisation. Frontal strain in the decatetraene plays an important part in influencing their stability.     

The free-radical reaction of tri-n-butyltin hydride with peroxides

Rate constants for the tri-n-butyltin radical ( Sn · ) induced decomposition of a number of peroxides have been measured in benzene at 10°C. The values range from ～100 M^?1 sec^?1 for di-t-butyl peroxide to 2.6 × 10⁷ M^?1 sec^?1 for di-t-butyl diperoxyisophthalate. The majority of the peroxides, including diethyl peroxide, diacetyl peroxide, and t-butyl peracetate, have rate constants of ～10⁵ M^?1 sec^?1. It is shown that di-n-alkyl disulfides are ten times as reactive toward Sn · as di-n-alkyl peroxides, although the exothermicities of these reactions are ～15 and ～39 kcal/mole, respectively. The enhanced reactivity of the disulfides is attributed to the easier formation of an intermediate or transition state with 9 electrons around sulfur, compared with an analogous species with 9 electrons around oxygen. The following bond strengths (kcal/mole) have been estimated: D[ Sn ? OR] = 77; D[ Sn ? H] = 82; D[ Sn ? SR] = 83; and D[ Sn ? OC(O)R] = 86, where R = alkyl. Rate constants for reaction of Sn · with some benzyl esters have also been measured. It has been found that t-butoxy radicals can add to benzene and abstract hydrogen from benzene at ambient temperatures.     

Thermodynamic anomalies in the presence of general linear dissipation: from the free particle to the harmonic oscillator

A free particle coupled to a heat bath can exhibit a number of thermodynamic anomalies like a negative specific heat, reentrant classicality or a nonmonotonic entropy. These low-temperature phenomena are expected to be modified at very low temperatures where finite-size effects associated with the discreteness of the energy spectrum become relevant. In this paper, we explore in which form the thermodynamic anomalies visible in the specific heat and the entropy of the free damped particle appear for a damped harmonic oscillator. Since the discreteness of the oscillator’s energy spectrum is fully accounted for, the results are valid for arbitrary temperatures. As expected, they are in agreement with the third law of thermodynamics and indicate how the thermodynamic anomalies of the free damped particle can be reconciled with the third law. Particular attention is paid to the transition from the harmonic oscillator to the free particle when the limit of the oscillator frequency to zero is taken.