Conformational stability of CH3CH2PH2BH3 from temperature dependent FT-IR spectra of xenon solutions and r0 structural parameters

Variable temperature (-55--100 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylphosphine-borane, CH3CH2PH2BH3, and ethylphosphine-borane-d5 dissolved in liquid xenon have been recorded. From these data, the enthalpy difference has been determined to be 86 +/- 8 cm(-1) (1.03 +/- 0.10 kJ/mol), with the trans conformer the more stable rotamer. Complete vibrational assignments are presented for both conformers, which are consistent with the predicted frequencies obtained from the ab initio MP2/6-31G(d) calculations. The optimized geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, and depolarization ratios have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations. These quantities are compared to the corresponding experimental quantities when appropriate as well as with some corresponding results for some similar molecules. The r0 structural parameters have been obtained from a combination of the previously reported microwave rotational constants and ab initio predicted parameters.     

Transition structure in a diabatic surface formalism

The theory of an implementation of the diabatic surface model within the Heitler–London valence bond approach is described. It is shown that the HL –VB wave function can be obtained from a Van-Vleck transformation of an MC –SCF wave function which has been built from atom-localized orbitals. This wave function is built from a superposition of two diabatic components, reactantlike and productlike. The transition structure is then obtained as the minimum of the seam of intersection of the diabatic surfaces and the algorithm for performing this constrained optimization is described. Several areas of application are also discussed.     

Formation and characterization of polymersomes made by a solvent injection method

In this article a solvent injection method is described for vesicle formation using poly(butadiene)‐ b‐poly(acrylic acid) diblock copolymers as the amphiphilic molecules. Vesicles composed of polymer bilayers are commonly referred to as polymersomes. Solvent injection is shown to be a rapid method for polymersome formation suitable to make large volumes of polymersome solution. The method can be manipulated to obtain a wide range of vesicle sizes depending on the polymer concentration and preparation conditions. Polymersome solutions in this study are characterized using dynamic light scattering (DLS), fluorescent microscopy, and electron microscopy. Polymersome sizes range from tens of nanometers to several microns. The membrane thickness of smaller polymersomes is found to lie between 14–20 nm. Larger polymersomes are found to have somewhat thicker membranes. The procedure involves the addition of polymers dissolved in an organic solvent to a stirred aqueous solution. The formation of polymersomes by this method is proposed to be governed by the limited mutual solubility of the two solvents and the simultaneous diffusion of solvent and water out of and in to initially formed organic solvent droplets. Copyright © 2007 John Wiley & Sons, Ltd.     

Relationship between photoisomerization path and intersection space in a retinal chromophore model

A low-lying segment of the intersection space (IS) between the excited-state and the ground-state energy surfaces of a retinal chromophore model has been mapped using ab initio CASSCF computations. Analysis of the structural relationship between the computed IS cross-section and the excited state Z --> E isomerization path shows that these are remarkably close both in energy and in structure. Indeed, the IS segment and the Z --> E path remain roughly parallel and merge only when the double bond reaches a 70 degree twisting. This finding supports the idea that, in certain chromophores, a more extended segment of IS, and not a single conical intersection, contributes to the decay to the ground state.     

Electrodeposited polythiophene films provide reproducible samples for laser desorption ion trap mass spectrometry studies

Electrodeposited polythiophene films can provide consistent laser desorption signal levels for over 20,000 laser shots on one position of a probe tip in an ion trap. A similar lack of signal decay was observed for multiple positions on the same film. The consistency and longevity of the ion signal resulting from laser desorption of a polythiophene film are much greater than those typically obtained from simple solution residue samples. Uniform, electrodeposited polythiophene films can provide a great reduction in the uncertainty of ion production that has previously been associated with ion trapping studies utilizing laser desorption.     

Analysis of coefficient identification problems associated to the inverse Euler-Bernoulli beam theory

A rigorous investigation of the identification of a heterogeneousflexural rigidity coefficient in the Euler-Bernoulli steady-statebeam theory in the presence of a prescribed load is presented.Mathematically, this study is an extension to higher-order differentialequations of the coefficient identification problem analysedby Marcellini (1982) for the one-dimensional Poisson equation.In addition, various types of boundary conditions are discussed.Conditions for the well-posedness of these inverse problemsare established and, furthermore, numerical results obtainedusing a regularization algorithm are presented.     

A critical investigation of the effects of the radio frequency potential on the trapping of externally injected ions in ion trap mass spectrometry

The sensitivity of all ion trap mass spectrometry (ITMS) methods is dependent on the trapping efficiency of the instrument. For ITMS instruments utilizing external ion sources, such as laser desorption, trapping efficiency is known to depend on the phase and amplitude of the radio frequency (RF) potential applied to the ring electrode at the time of ion introduction. It is remarkable that, in a considerable body of literature, no consensus exists regarding the effects of these parameters on the efficacy of trapping externally generated ions. In this paper, a summary of the literature is presented in order to highlight significant discrepancies. New laser desorption ion trap mass spectrometry (LD-ITMS) data are also presented, from which conclusions are drawn in our effort to clarify some of the confusion. Copyright 1999 John Wiley & Sons, Ltd.     

Singlet excited-state dynamics of 5-fluorocytosine and Cytosine: an experimental and computational study

The photophysics of singlet excited 5-fluorocytosine (5FC) was studied in steady-state and time-resolved experiments and theoretically by quantum chemical calculations. Femtosecond transient absorption measurements show that replacement of the C5 hydrogen of cytosine by fluorine increases the excited-state lifetime by 2 orders of magnitude from 720 fs to 73 +/- 4 ps. Experimental evidence indicates that emission in both compounds originates from a single tautomeric form. The lifetime of 5FC is the same within experimental uncertainty in the solvents ethanol and dimethyl sulfoxide. The insensitivity of the S(1) lifetime to the protic nature of the solvent suggests that proton transfer is not the principal quenching mechanism for the excited state. Excited-state calculations were carried out for the amino-keto tautomer of 5FC, the dominant species in polar environments, in order to understand its longer excited-state lifetime. CASSCF and CAS-PT2 calculations of the excited states show that the minimum energy path connecting the minimum of the (1)pi,pi state with the conical intersection responsible for internal conversion has essentially the same energetics for cytosine and 5FC, suggesting that both bases decay nonradiatively by the same mechanism. The dramatic difference in lifetimes may be due to subtle changes along the decay coordinate. A possible reason may be differences in the intramolecular vibrational redistribution rate from the Franck-Condon active, in-plane modes to the out-of-plane modes that must be activated to reach the conical intersection region.     

Perturbed smooth Lipschitz extensions of uniformly continuous functions on Banach spaces

We show that if is a separable subspace of a Banach space such that both and the quotient have -smooth Lipschitz bump functions, and is a bounded open subset of , then, for every uniformly continuous function and every 0$">, there exists a -smooth Lipschitz function such that for every .