Conformational composition of cyclopentadienylphosphine investigated by microwave spectroscopy and quantum chemical calculations

The properties of cyclopentadienylphosphine have been investigated by means of Stark-modulation microwave spectroscopy and quantum chemical calculations at the MP2/aug-cc-pVTZ, B3LYP/6-311++G(d,p), and G3 levels of theory. Spectra attributable to two rotamers denoted conformers I and II have been assigned. Conformer I has a symmetry plane (Cs symmetry) consisting of the bisectors of the cyclopentadiene ring and of the phosphino group with the lone electron pair of phosphorus pointing toward the carbon ring. In conformer II, the phosphino group is rotated approximately 120 degrees out of this plane. Relative intensity measurements have been made, and it was found that conformer II is more stable than I by 1.3(4) kJ/mol. The preferred conformer represents a borderline case of intramolecular hydrogen bond stabilization. The experimental and MP2/ aug-cc-pVTZ rotational constants differ by several percent, which indicates that the aug-cc-pVTZ basis set is not large enough to be able to predict an accurate structure for the two conformers that are close to the equilibrium geometries. 5-Substituted 1,3-cyclopentadienyl derivatives may undergo circumambulatory rearrangements. However, there is no manifestation of this effect in the microwave spectrum of cyclopentadienylphosphine.     

Can cluster structure affect kinetic method measurements? The curious case of glutamic acid’s gas-phase acidity

The gas-phase acidities of aspartic, glutamic, and 2-aminoadipic acid have been determined by the kinetic method in a triple-quadrupole instrument. Although aspartic acid behaves in the conventional way and gives a DeltaH(acid) value of 1340 kJ mol(-1), glutamic and 2-aminoadipic acids give kinetic method plots with two distinct slopes. This leads to DeltaH(acid) values of 1350 and 1366 kJ mol(-1) for glutamic acid, and 1355 and 1369 kJ mol(-1) for 2-aminoadipic acid. The value for aspartic acid and the low collision energy value for glutamic acid are consistent with recent measurements by Poutsma and co-workers in a quadrupole ion trap. The experiments are supported by calculations at the G3(MP2) and OLYP/aug-cc-pVTZ levels. Computational studies of model clusters of the amino acids with trifluoroacetate suggest there are distinct preferences. Glutamic and 2-aminoadipic acid prefer clusters where the amino acid adopts a zwitterion-like structure whereas aspartic acid prefers to adopt a conventional (canonic) structure in its clusters. This result along with the computed stabilities of zwitterion-like conformations of the deprotonated amino acids leads to the following explanation for the presence of two slopes in the kinetic method plots. At low collision energies, the deprotonated amino acid dissociates from the cluster, with rearrangement if necessary, to give its preferred conformation, but at high collision energies, the deprotonated amino acid directly dissociates in the conformation preferred in the cluster. For glutamic and 2-aminoadipic acids, this is a zwitterion-like structure that is about 20 kJ mol(-1) less stable than the global minimum.     

Ni+ reactions with aminoacrylonitrile, a species of potential astrochemical relevance

The reaction of aminoacrylonitrile, a species of astrochemical interest, with Ni(+)((2)D(5/2)) was investigated by means of mass spectrometry techniques and density functional theory calculations. The dominant fragmentations in the MIKE spectrum correspond to the loss of [C2,N,H3], HCN, and NH3, the loss of H2 being very minor. The structure and bonding of the different aminoacrylonitrile-Ni(+) complexes were investigated at the B3LYP/6-311G(d,p) level of theory. The same approach was employed in our survey of the corresponding potential energy surface. This survey indicates that the [C2,N,H3] neutral product can be formed either as ketenimine (CH2CNH) or acetonitrile. The formation of the latter is significantly more exothermic but involves slightly higher activation barriers; so very likely, both isomers are produced along the reaction process. The lost of HNC is not competitive with the loss of HCN, because when the former is formed the products lie higher in energy and the corresponding mechanisms involve energy barriers above the entrance channel. The loss of NH3 is associated with the formation of a complex between cyanoacetylene, HCCCN, which is very abundant in the interstellar media, and Ni(+).     

Global Existence of Small Solutions to a Relativistic Nonlinear Schrödinger Equation

Résumé: On étudie le problème de Cauchy associéà une equation de Schr?dinger non linéaire modélisant une impulsion laser ultra-intense et ultra-courte dans un plasma. Les termes non linéaires nouveaux sont d?s aux effets relativistes et à la force pondéromotrice. Nous prouvons l'existence locale et l'unicité de solutions petites lorsque la dimension de l'espace transverse est égale à 2 ou 3, ainsi que l'existence locale pour des données initiales de taille arbitraire, en dimension un d'espace transverse. We study the Cauchy problem associated to a nonlinear Schr?dinger equation modelling the self-channeling of a high power, ultra-short laser pulse in matter. The new nonlinear terms arise from relativistic effects and from the ponderomotive force. We prove global existence and uniqueness of small solutions in transverse space dimensions 2 and 3, and local existence without any smallness condition in transverse space dimension 1. Received: 2 December 1996 / Accepted: 24 February 1997     

Identification of the 'wrong' active pharmaceutical ingredient in a counterfeit Halfan drug product using accurate mass electrospray ionisation mass spectrometry,accurate mass tandem mass spectrometry and liquid chromatography/mass spectrometry

Methodology is presented for identifying an unknown active (pharmaceutical) ingredient (AI) in a counterfeit drug product. A range of mass spectrometric techniques, i.e., accurate mass mass spectrometry, tandem mass spectrometry (MS/MS) and liquid chromatography/mass spectrometry (LC/MS), has been employed to determine the AI in a counterfeit Halfan suspension, an antimalarial drug. In particular, use of LockSpray accurate mass MS/MS allowed identification of parts of the molecule from fragments, hence limiting the number of possible elemental compositions for the nominal mass of 278 found for the AI in the counterfeit product. The analysis of the isotope pattern observed for the protonated molecule further reduced the number of possible elemental compositions. A literature search for readily commercially available compounds of molecular formula C(12)H(14)N(4)O(2)S suggested that the AI was either sulfamethazine or sulfisomidine. An LC/MS separation of those two compounds and reference MS/MS spectra obtained for sulfamethazine and sulfisomidine led to the conclusion that the AI in the counterfeit Halfan suspension is sulfamethazine, which is an antibacterial agent.     

Origin of the red shifts in the optical absorption bands of nonplanar tetraalkylporphyrins

The view that the large red shifts seen in the UV-visible absorption bands of peripherally crowded nonplanar porphyrins are the result of nonplanar deformations of the macrocycle has recently been challenged by the suggestion that the red shifts arise from substituent-induced changes in the macrocycle bond lengths and bond angles, termed in-plane nuclear reorganization (IPNR). We have analyzed the contributions to the UV-visible band shifts in a series of nickel or zinc meso-tetraalkylporphyrins to establish the origins of the red shifts in these ruffled porphyrins. Structures were obtained using a molecular mechanics force field optimized for porphyrins, and the nonplanar deformations were quantified by using normal-coordinate structural decomposition (NSD). Transition energies were calculated by the INDO/S semiempirical method. These computational studies demonstrate conclusively that the large Soret band red shifts ( approximately 40 nm) seen for very nonplanar meso-tetra(tert-butyl)porphyrin compared to meso-tetra(methyl)porphyrin are primarily the result of nonplanar deformations and not IPNR. Strikingly, nonplanar deformations along the high-frequency 2B(1u) and 3B(1u) normal coordinates of the macrocycle are shown to contribute significantly to the observed red shifts, even though these deformations are an order of magnitude smaller than the observed ruffling (1B(1u)) deformation. Other structural and electronic influences on the UV-visible band shifts are discussed and problems with the recent studies are examined (e.g., the systematic underestimation of the 2B(1u) and 3B(1u) modes in artificially constrained porphyrin structures that leads to a mistaken attribution of the red shift to IPNR). The effect of nonplanar deformations on the UV-visible absorption bands is then probed experimentally with a series of novel bridled nickel chiroporphyrins. In these compounds, the substituent effect is essentially invariant and the amount of nonplanar deformation decreases as the length of the straps connecting adjacent meso-cyclopropyl substituents decreases (the opposite of the effect observed for conventional strapped porphyrins). Several spectroscopic markers for nonplanarity (UV-visible bands, resonance Raman lines, and (1)H NMR resonances) are found to correlate with time-averaged deformations obtained from an NSD analysis of molecular dynamics snapshot structures. These results suggest that UV-visible band shifts of tetrapyrroles in proteins are potentially useful indicators of changes in nonplanarity provided other structural and electronic factors can be eliminated.     

Raman scattering study of the ferroelectric phase transition in tris-sarcosine calcium chloride (tscc)

We obtained Raman scattering spectra of normal and deuterated TSCC crystals and one TSCC_I-xB_x mixed crystal (c_I-x = Cl, B_x = Br). The soft-mode behaviour is studied in the temperature range from 80 K to the Curie point. The L and T component of the soft mode are overdamped near 100 K while the oblique component can be observed all over the temperature range we studied. For both normal TSCC and mixed TSCC_I-xB_x crystals the critical exponent β = $\text{1}\text{3}$ is in agreement with dielectric measurements and theoretical calculations.     

Paramagnetic defects in α-WxV2O5

Paramagnetic defects in α-W_xV₂O₅ have been studied by ESR. A model is proposed where the unpaired electron arising from a valence induction effect remains localized on a single vanadium ion near the W⁶⁺ along the b direction. Introducing W⁶⁺ leads to a lattice distortion which is more important than that in the case of Mo⁶⁺. A slight displacement of vanadium along the a direction is observed in the defect, V⁴⁺ showing a stronger tendency toward octahedral coordination than V⁵⁺.     

On the existence of the protonated hydronium dication H4O in sulfolane solution

The enthalpy of solvation in sulfolane of the gaseous protonated hydronium dication is estimated as −628 kcal/mol at 298 K. Using literature data, a value ΔH^o = −212 kcal/mol is calculated for the reaction H₃O⁺ + H⁺→ H₄O²⁺ (in sulfolane), supporting the thermodynamic existence of H₄O²⁺ in sulfolane solution, as characterized previously by potentiometric and conductometric titrations. Some aspects of these results are discussed.