The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Ion imaging coupled with (2 + 1) resonance-enhanced multiphoton ionization (REMPI) technique is employed to probe CO(v″ = 0) fragments at different rotational levels following photodissociation of methyl formate (HCOOCH(3)) at 234 nm. When the rotational level, J″(CO), is larger than 24, only a broad translational energy distribution extending beyond 70 kcal mol(-1) with an average energy of about 23 kcal mol(-1) appears. The dissociation process is initiated on the energetic ground state HCOOCH(3) that surpasses a tight transition state along the reaction coordinate prior to breaking into CO + CH(3)OH. This molecular dissociation pathway accounts for the CO fragment with larger rotational energy and large translational energy. As J″(CO) decreases, a bimodal distribution arises with one broad component and the other sharp component carrying the average energy of only 1-2 kcal mol(-1). The branching ratio of the sharp component increases with a decrease of J″(CO); (7.3 ± 0.6)% is reached as the image is probed at J″(CO) = 10. The production of a sharp component is ascribed to a roaming mechanism that has the following features: a small total translational energy, a low rotational energy partitioning in CO, but a large internal energy in the CH(3)OH co-product. The internal energy deposition in the fragments shows distinct difference from those via the conventional transition state.

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By using time-resolved Fourier-transform infrared emission spectroscopy, the fragments of HCN(v = 1, 2) and CO(v = 1-3) are detected in one-photon dissociation of acetyl cyanide (CH(3)COCN) at 308 nm. The S(1)(A(")), (1)(n(O), π(∗) (CO)) state at 308 nm has a radiative lifetime of 0.46 ± 0.01 μs, long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of Ar collision-induced internal conversion is estimated to be (1-7) × 10(-12) cm(3) molecule(-1) s(-1). The measurements of O(2) dependence exclude the production possibility of these fragments via intersystem crossing. The high-resolution spectra of HCN and CO are analyzed to determine the ro-vibrational energy deposition of 81 ± 7 and 32 ± 3 kJ∕mol, respectively. With the aid of ab initio calculations, a two-body dissociation on the energetic ground state is favored leading to HCN + CH(2)CO, in which the CH(2)CO moiety may further undergo secondary dissociation to release CO. The production of CO(2) in the reaction with O(2) confirms existence of CH(2) and a secondary reaction product of CO. The HNC fragment is identified but cannot be assigned, as restricted to a poor signal-to-noise ratio. Because of insufficient excitation energy at 308 nm, the CN and CH(3) fragments that dominate the dissociation products at 193 nm are not detected.

Single-molecule fluorescence correlation spectroscopy overcomes the resolution barrier of optical microscopy (10≈-20 nm) and is utilized to look into lipid dynamics in small unilamellar vesicles (SUVs; diameter < 100 nm). The fluorescence trajectories of lipid-like tracer 1,1'-dioctadecyl-3,3,3',3'-tetramethylindodicarbocyanine (DiD) in the membrane bilayers are acquired at a single-molecule level. The autocorrelation analysis yields the kinetic information on lipid organization, oxygen transport, and lateral diffusion in SUVs' membrane. First, the isomerization feasibility may be restricted by the addition of cholesterols, which form structure conjugation with DiD chromophore. Second, the oxygen transport is prevented from the ultrasmall cluster and cholesterol-rich regions, whereas it can pass through the membrane region with liquid-disordered phase (L ) and defects. Third, by analyzing 2D spectra correlating the lipid diffusion coefficient and triplet-state lifetime, the heterogeneity in lipid bilayer can be precisely visualized such as lipid domain with different phases, the defects of lipid packing, and DiD-induced "bouquet" ultrasmall clusters.

Competitive bond dissociation mechanisms for bromoacetyl chloride and 2- and 3-bromopropionyl chloride following the (1) [n(O)→π*(C=O)] transition at 234-235 nm are investigated. Branching ratios for C−Br/C−Cl bond fission are found by using the (2+1) resonance-enhanced multiphoton ionization (REMPI) technique coupled with velocity ion imaging. The fragment branching ratios depend mainly on the dissociation pathways and the distances between the orbitals of Br and the C=O chromophore. C−Cl bond fission is anticipated to follow an adiabatic potential surface for a strong diabatic coupling between the n(O)π*(C=O) and np (Cl)σ*(C−Cl) bands. In contrast, C−Br bond fission is subject to much weaker coupling between n(O)π*(C=O) and np (Br)σ*(C−Br). Thus, a diabatic pathway is preferred for bromoacetyl chloride and 2-bromopropionyl chloride, which leads to excited-state products. For 3-bromopropionyl chloride, the available energy is not high enough to reach the excited-state products such that C−Br bond fission must proceed through an adiabatic pathway with severe suppression by nonadiabatic coupling. The fragment translational energies and anisotropy parameters for the three molecules are also analyzed and appropriately interpreted.

By using photofragment velocity imaging detection coupled with a (2 + 1) resonance-enhanced multiphoton ionization technique, the elimination channel of spin-orbit chlorine atoms in photodissociation of cis-, trans-, and 1,1-dichloroethylene at two photolysis wavelengths of 214.5 and 235 nm is investigated. Translational energy and angular distributions of Cl((2)P(J)) fragmentation are acquired. The Cl((2)P(J)) fragments are produced by two competing channels. The fast dissociation component with higher translational energy is characterized by a Gaussian distribution, resulting from a curve crossing of the initially excited (pi, pi*) state to nearby repulsive (pi, sigma*) and/or (n, sigma*). In contrast, the slow component with a lower translational energy is characterized by a Boltzmann distribution, which dissociates on the vibrationally hot ground state relaxed from the (pi, pi*) state via internal conversion. cis-C(2)H(2)Cl(2) is found to have a larger branching of Boltzmann component than the other two isomers. The fraction of available energy partitioning into translation increases along the trend of cis- < trans- < 1,1-C(2)H(2)Cl(2). This trend may be fitted by a rigid radical model and interpreted by means of a torque generated during the C-Cl bond cleavage. The anisotropy parameters are determined, and the transition dipole moments are expected to be essentially along the C horizontal lineC bond axis. The results are also predicted theoretically. The relative quantum yields of Cl((2)P(J)) have a similar value for the three isomers at the two photolysis wavelengths.

Quantum decoherence can be viewed as the mechanism responsible for the quantum-to-classical transition as the initially prepared quantum state interacts with its environment in an irreversible manner. One of the most common mechanisms responsible for the macroscopically observed decoherence involves collisions of an atom or molecule, initially prepared in a coherent superposition of states, with gas particles. In this work, a coherent superposition of quantum internal states of NO molecules is prepared by the interaction between the molecule with both a static and a radiofrequency electric field. Subsequently, NO + Ar collision decoherence experiments are investigated by measuring the loss of coherence as a function of the number of collisions. Data analysis using a model based on the interaction potential of the collisional partners allowed to unravel the molecular mechanism responsible for the loss of coherence in the prepared NO quantum superposition of internal states. The relevance of the present work relies on several aspects. On the one hand, the use of radio-waves introduces a new way for the production of coherent beams. On the other hand, the employed methodology could be useful in investigating the Stereodynamics of chemical reactions with coherent reagents.