Distance Dependence of Nonadiabaticity in the Branching Between C–Br and C–Cl Bond Fission Following 1[n(O),π∗(C=O)] Excitation in Bromopropionyl Chloride

These experiments on bromopropionyl chloride investigate a system in which the barrier to C-Br fission on the lowest 1A\u27\u27 potential energy surface is formed from a weakly avoided electronic configuration crossing, so that nonadiabatic recrossing of the barrier to C-Br fission dramatically reduces the branching to C-Br fission. The results, when compared with earlier branching ratio measurements on bromoacetyl chloride, show that the additional intervening CH2 spacer in bromopropionyl chloride reduces the splitting between the adiabatic potential energy surfaces at the barrier to C-Br fission, further suppressing C-Br fission by over an order of magnitude. The experiment measures the photofragment velocity and angular distributions from the 248 nm photodissociation of Br (CH2)2COCl, determining the branching ratio between the competing primary C-Br and C-Cl fission pathways and detecting a minor C-C bond fission pathway. While the primary C-Cl:C-Br fission branching ratio is 1:2, the distribution of relative kinetic energies impar-ted to the C-Br fission fragments show that essentially no C-Br fission results from promoting the molecule to the lowest 1A\u27\u27 potential energy surface via the 1[n(O),pi*(C-O)] transition; C-Br fission only results from an overlapping electronic transition. The results differ markedly from the predictions of statistical transition state theories which rely on the Born-Oppenheimer approximation. While such models predict that, given comparable preexponential factors, the reaction pathway with the lowest energetic barrier on the 1A\u27\u27 surface, C-Br fission, should dominate, the experimental measurements show C-Cl bond fission dominates by a ratio of C-Cl:C-Br=1.0: \u3c0.05 upon excitation of the 1[n(O),pi*(C=O)] transition. We compare this result to earlier work on bromoacetyl chloride, which evidences a less dramatic reduction in the C-Br fission pathway (C-Cl:C-Br = 1.0:0.4) upon excitation of the same transition. We discuss a model in which increasing the distance between the C-Br and C=O chromophores decreases the electronic configuration interaction matrix elements which mix and split the 1n(O)pi*(C=O) and np(Br)sigma*(C-Br) configurations at the barrier to C-Br bond fission in bromopropionyl chloride. The smaller splitting between the adiabats at the barrier to C-Br fission increases the probability of nonadiabatic recrossing of the barrier, nearly completely suppressing C-Br bond fission in bromopropionyl chloride. Preliminary ah initio calculations of the adiabatic barrier heights and the electronic configuration interaction matrix elements which split the adiabats at the barrier to C-Br and C-Cl fission in both bromopropionyl chloride and bromoacetyl chloride support the interpretation of the experimental results. We end by identifying a class of reactions, those allowed by overall electronic symmetry but Woodward-Hoffmann forbidden, in which nonadiabatic recrossing of the reaction barrier should markedly reduce the rate constant, both for ground state and excited state surfaces

Competing C–Br and C–C Bond Fission Following 1[n(O),π∗(C=O)] Excitation in Bromoacetone: Conformation Dependence of Nonadiabaticity at a Conical Intersection

These experiments investigate the competition between C-C and C-Br bond fission in bromoacetone excited in the (1)[n(O),pi(*)(C=O)] absorption, elucidating the role of molecular conformation in influencing the probability of adiabatically traversing the conical intersection along the C-C fission reaction coordinate. In the first part of the paper, measurement of the photofragment velocity and angular distributions with a crossed laser-molecular beam time-of-flight technique identifies the primary photofragmentation channels at 308 nm. The time-of-flight spectra evidence two dissociation channels, C-Br fission and fission of one of the two C-C bonds, BrH2C-COCH3. The distribution of relative kinetic energies imparted to the C-Br fission and C-C fission fragments show dissociation is not occurring via internal conversion to the ground electronic state and allow us to identify these channels in the closely related systems of bromoacetyl- and bromopropionyl chloride. In the second part of the work we focus on the marked conformation dependence to the branching between C-C fission and C-Br fission. Photofragment angular distribution measurements show that C-Br fission occurs primarily from the minor, anti, conformer, giving a beta of 0.8, so C-C fission must dominate the competition in the gauche conformer. Noting that the dynamics of these two bond fission pathways are expected to be strongly influenced by nonadiabatic recrossing of the reaction barriers, we investigate the possible mechanisms for the conformation dependence of the nonadiabatic recrossing with low-level ab initio electronic structure calculations on the C-Br reaction coordinate and qualitative consideration of the conical intersection along the C-C reaction coordinate. The resulting model proposes that C-C bond fission,cannot compete with C-Br fission in the anti conformer because the dissociation samples regions of the phase space near the conical intersection along the CC fission reaction coordinate, where nonadiabaticity inhibits C-C fission, while from the gauche conformer C-C fission can proceed more adiabatically and dominate C-Br fission. A final experiment confirms that the branching ratio changes with the relative conformer populations in accord with this model

Ultrahigh sensitivity of slow-light gyroscope

Slow light generated by Electromagnetically Induced Transparency is extremely susceptible with respect to Doppler detuning. Consequently, slow-light gyroscopes should have ultrahigh sensitivity

Ultrafast Coherent Generation of Hot Electrons Studied via Band-to-Acceptor Luminescence in GaAs

The distribution of hot electrons excited with femtosecond laser pulses is studied via spectrally resolved band-to-acceptor luminescence. Our data demonstrate for the first time that the coherent coupling between the laser pulse and the interband polarization strongly influences the initial carrier distribution. The energetic width of carrier generation is broadened due to rapid phase-breaking scattering events. Theoretical results from a Monte Carlo solution of the semiconductor Bloch equations including on the same kinetic level coherent and incoherent phenomena, are in excellent agreement with the experimental data

Chemical Displacement of Molecules Adsorbed on Copper Surfaces: Low-Temperature Studies with Applications to Surface Reactions

Previous experiments have demonstrated that displacement of a molecule adsorbed on a metal surface by an impinging gas-phase molecule can be quite a facile process. The generality of this process for an enthalpic driving force as small as 1 kcal/mol is demonstrated here using the displacement of a weakly binding alkene, cyclopentene, by a series of more strongly binding alkenes on Cu(100). Surface structure sensitivity in the process is also demonstrated by a comparison of benzene and cyclopentene coadsorption on Cu(100) and Cu(110). This work also shows the utility of conducting the displacement process below the temperature at which the displaced molecule desorbs from the multilayer so that temperature-programmed desorption can be used to quantify the surface coverage of displaced molecules. It is also shown that one can readily determine the kinetics of adsorbate bond dissociation and bond formation reactions by combining these chemical displacement measurements of surface coverage with an anneal/quench protocol. This approach is demonstrated through chemical displacement experiments that determine that the C-Br bond in vinyl bromide adsorbed on Cu(100) dissociates near 157 K and that the formation of toluene from reaction between methyl iodide and coadsorbed phenyl groups on Cu(110) occurs below 160 K. The relative importance of enthalpy and entropy in chemical displacement is also discussed

Relativistic Effects of Light in Moving Media with Extremely Low Group Velocity

A moving dielectric medium acts as an effective gravitational field on light. One can use media with extremely low group velocities [Lene Vestergaard Hau et al., Nature 397, 594 (1999)] to create dielectric analogs of astronomical effects on Earth. In particular, a vortex flow imprints a long-ranging topological effect on incident light and can behave like an optical black hole.Comment: Physical Review Letters (accepted

Moderate Alcohol Drinking and the Amygdala Proteome: Identification and Validation of Calcium/Calmodulin Dependent Kinase II and AMPA Receptor Activity as Novel Molecular Mechanisms of the Positive Reinforcing Effects of Alcohol

Despite worldwide consumption of moderate amounts of alcohol, the neural mechanisms that mediate the transition from use to abuse are not fully understood