Stretching-mode specificity in the Cl + CH3D(v1-I, v1-II, and v4 = 1; |jK〉) reactions: dependency on the initial |jK〉 selectivity.

The title reactions were studied at a collisional energy of 5.4 kcal mol-1 in a crossed-beam product-imaging experiment. The dynamics attributes of the dominant ground-state CH2D(00) and the accompanied C-D bend-excited CH2D(61) products were imaged in reactions with totally 16 ro-vibrationally selected states of the CH3D(vi, |jK〉) reagents. We found that all three vibrational excitations yielded marked |jK〉-dependent rate-enhancements in forming the (00, 0/1)s product pairs. Furthermore, for a given rotational |jK〉-mode, a vibrational-mode propensity of v4 > v1-I > v1-II in rate promotion and a clear manifestation of the Fermi-phase-induced interference effect of the latter two were observed. Compared to the reactivity of the rotationless state |jK〉 = |00〉, a minute rotational-excitation of all three stretch-excited CH3D(vi = 1) reagents could yield significantly higher reaction rates for the product pair (00, 0)s, but not so for (00, 1)s. The signals in forming the (61, 0)s pair were clearly notable but smaller than that of the ground-state reaction product pair, (00, 0)g. An opposite propensity of v1-II ≈ v1-I > v4 with a milder dependency on the initial |jK〉-states was observed. The angular distributions of the (00, 0)s pairs were nearly identical for all ro-vibrationally excited reagents, displaying the typical trait for a direct abstraction of the rebound mechanism. Similar distributions were found for the (61, 0)s pairs; yet, both pairs deviated substantially from the peripheral feature of the ground-state reaction pair of (00, 0)g. Those of the (00, 1)s pairs in reactions with v4-excitation featured a prominent forward-peaking distribution-suggestive of a time-delayed, resonance-mediated pathway, again with little dependency on the initial |jK〉-states. As for the reactions with the two Fermi-dyads, v1-I and v1-II, albeit showing globally similar distributions to that for v4, a substantial variation with the initial rotational-mode excitation could be discerned in the forward-peaking features. To unravel the impact of the Fermi-phase on the |jK〉-dependent attributes, we adopted a comparative approach by contrasting the observations in reactions with the Fermi-dyad reagents (the superposition states) to those with the pure-state reagents. Remarkable distinctions are unveiled and elucidated with the unexplained results explicitly pointed out, which call for future theoretical investigations for deeper understanding.

Imaging the Mode-Specificity in Cl + CH3D(v1-I, v1-II, v4 = 1; |jK⟩ = |10⟩) → CH2D(41) + HCl(v).

We report a crossed-beam imaging experiment on the title reactions at two collisional energies (Ec) of 5.3 and 10 kcal mol-1. Both the integral cross sections relative to the ground-state reactivity and the differential cross sections were measured and compared. We found that one-quantum excitations of the CH3-stretching vibrations of the CH3D reagent exerted profound mode-specificity in forming the umbrella-mode-excited CH2D(41) products with the vibrational efficacy of v4 > v1-I > v1-II at both Ec values. The concomitantly formed HCl(v) coproducts were vibrationally cold. Interestingly, the branching ratios of (v = 1)/(v = 0) appeared invariant to the initial stretch-modes of excitation at Ec = 5.3 kcal mol-1, yet exhibited a pronounced mode-specific dependency in the order of v1-II > v1-I > v4 at Ec = 10.3 kcal mol-1. This large and Ec-dependent disparity between the two Fermi-coupled reagents, v1-I and v1-II, is particularly significant and could be another facet─in addition to that in the recently reported vibrational enhancement factors─of the Fermi-phase-induced interference effect manifested in the product vibrational branching ratio. The pair-correlated angular distributions (vCH2D, vHCl)s = (41, 0)s in the three stretch-excited reactions were globally alike and resembled that of the ground-state reaction pair (00, 0)g, suggestive of a direct abstraction mechanism of the peripheral type. This is in sharp contrast to all other vibrationally excited pairs of (11, 0)s, (31, 0)s, and (61, 0)s previously reported in the CH2D + HCl isotopic channel, for which both the direct abstraction and a time-delayed resonance pathway partake.

Hydrogen-Bonded Complexes of Fluorophenylacetylenes: To Fluoresce or Not?

The hydrogen-bonded complexes of fluorophenylacetylenesexhibit unusual and interesting fluorescence turn ON/OFF behaviour following excitation to 1 ππ* (S1 ) state. The fluorescence switching behaviour can be realized by (i) "change in the intermolecular structure, (ii) change in the position of fluorine substitution and (iii) change in the hydrogen bonding partner or a combination thereof. Experiments indicate that the ≡C-H⋅⋅⋅X (X=O, N) hydrogen bonding with the acetylenic group plays a pivotal role in this switching behaviour. Intriguingly, weaker ≡C-H⋅⋅⋅X hydrogen bonding leads to fluorescence OFF state, which is turned ON by stronger hydrogen bonding. The observed fluorescence this switching behaviour is rationalized on the basis of a phenomenological model which suggests a coupling between the initially excited S1 state and a dark Sn state in the Franck-Condon region with limited window controlled by the ≡C-H⋅⋅⋅X hydrogen bonding as a crucial parameter. Such fluorescence switching behaviour in hydrogen-bonded complexes is unprecedented and these intriguing results hopefully will stimulate theoreticians to test 'state of the art' theories to explain these observations in a consistent manner.

Effects of Stretching Excitations in Cl + CH3D( v4, v1-I, v1-II = 1): As the Cl Atom Attacks the Unexcited C-D Bond.

The title reactions were studied at two collisional energies ( Ec) in a crossed-beam product-imaging experiment. We found that all three initial CH stretching excitations suppress the reactivity toward the abstraction of the unexcited D atom. In terms of vibrational suppression factor, σs/σg, the product channels of CH3(00/41) + DCl and CH3(11/31) + DCl show opposite mode-specific trends. However, the angular distributions of both channels are nearly identical to that of the ground-state reaction at the same Ec, regardless of the initial reactant states. Tentatively, we ascribed these two observations to a vibrationally induced narrowing effect of the attack angle near the barrier to reaction. As for the DCl coproduct state distributions, the two channels are distinct but show little mode-specific difference. When CH3(00) is probed, the DCl coproduct peaks at v = 1 are accompanied by substantial rotational excitation, whereas the DCl products associated with CH3(11/31) are both vibrationally and rotationally cold. We attributed the different (correlated) energy disposals to a manifestation of trajectory bifurcations in the postbarrier region, with a vibrationally nonadiabatic pathway leading to CH3(00) + DCl( v = 1) and the other adiabatically to the CH3(11/31) + DCl( v = 0) channel. For both pathways the initial CH stretching excitation acts as a conserved mode by preferentially retaining one quantum of vibrational excitation in the reaction.

π-Stacked Dimers of Fluorophenylacetylenes: Role of Dipole Moment.

The homodimers of singly fluorine-substituted phenylacetylenes were investigated using electronic and vibrational spectroscopic methods in combination with density functional theory calculations. The IR spectra in the acetylenic C-H stretching region show a marginal red shift for the dimers relative to the monomers. Further, the marginal red shifts indicate that the acetylenic group in all the dimers is minimally perturbed relative to the corresponding monomer. The observed spectra were assigned to a set of π-stacked structures within an energy range of 1.5 kJ mol-1, which differ in the relative orientation of the two monomers on the basis of M06-2X/aug-cc-pVTZ level calculation. The observed red shift in the acetylenic C-H stretching vibration of the dimers suggests that the antiparallel structures contribute predominantly based on a simple coupled dipole model. Energy decomposition analysis using symmetry-adapted perturbation theory indicates that dispersion plays a pivotal role in π-π stacking with appreciable contribution of electrostatics. The stabilization energies of fluorophenylacetylene dimers follow the same ordering as their dipole moments, which suggests that dipole moment enhances the ability to form π-stacked structures.

Imaging characterization of the rapid adiabatic passage in a source-rotatable, crossed-beam scattering experiment.

In order to achieve a more efficient preparation of a specific ro-vibrationally excited reactant state for reactive scattering experiments, we implemented the rapid adiabatic passage (RAP) scheme to our pulsed crossed-beam machine, using a single-mode, continuous-wave mid-infrared laser. The challenge for this source-rotatable apparatus lies in the non-orthogonal geometry between the molecular beam and the laser propagation directions. As such, the velocity spread of the supersonic beam results in a significantly broader Doppler distribution that needs to be activated for RAP to occur than the conventional orthogonal configuration. In this report, we detail our approach to shifting, locking, and stabilizing the absolute mid-infrared frequency. We exploited the imaging detection technique to characterize the RAP process and to quantify the excitation efficiency. We showed that with appropriate focusing of the IR laser, a nearly complete population transfer can still be achieved in favorable cases. Compared to our previous setup-a pulsed optical parametric oscillator/amplifier in combination with a multipass ring reflector for saturated absorption, the present RAP scheme with a single-pass, continuous-wave laser yields noticeably higher population-transfer efficiency.

Spectroscopic and Ab†Initio Investigation of C-H⋠⋠⋠N Hydrogen-Bonded Complexes of Fluorophenylacetylenes: Frequency Shifts and Correlations.

The C-H⋅⋅⋅N hydrogen-bonded complexes of several fluorophenyacetylenes with ammonia and methylamine were characterized by a redshift in the acetylenic C-H stretching vibration of the phenylacetylene moiety. These redshifts were linearly correlated with the stabilization energies calculated at the CCSD(T)/CBS//MP2-aug-cc-pVDZ level. Analysis of various components of the interaction energy indicated that the observed redshifts were weakly correlated with the electrostatic component. The weaker linear correlation between the frequency shifts and the electrostatic component between two data sets can perhaps be attributed to the marginal differences in the Stark tuning rate and zero-field shifts. The induction and exchange-repulsion components were linearly correlated. However, the dispersion component depends on the nature of the hydrogen-bond acceptor and shows a quantum jump when the hydrogen-bond acceptor is changed from ammonia to methylamine. The observed linear correlation between the redshifts in the C-H stretching frequencies and the total stabilization energies is due to mutual cancellation of deviations from linearity between various components.

Spectroscopic and ab initio investigation of 2,6-difluorophenylacetylene-amine complexes: coexistence of C-H···N and lone-pair···π complexes and intermolecular coulombic decay.

Binary complexes of 2,6-difluorophenylacetylene with methylamine, dimethylamine, trimethylamine and triethylamine were investigated using one colour resonant two photon ionization and infrared-optical double resonance spectroscopic techniques combined with high level ab initio calculations. All four amines form CAc-H···N hydrogen-bonded complexes. Additionally trimethylamine and triethylamine form complexes characterized by Lp···π interactions, due to the electron deficient nature of the phenyl ring of 2,6-difluorophenylacetylene. The Lp···π interacting structure of the 2,6-difluorophenylacetylene-trimethylamine complex is about 1.5 kJ mol(-1) higher in energy than the CAc-H···N hydrogen-bonded structure, which is the global minimum. Energy decomposition analysis indicates that the electrostatics and dispersion interactions favour the formation of CAc-H···N and Lp···π complexes, respectively. Interestingly the CAc-H···N hydrogen-bonded complex of 2,6-difluorophenylacetylene-triethylamine showed a smaller shift in the acetylenic C-H stretching frequency than the 2,6-difluorophenylacetylene-trimethylamine complex. The observed fragmentation of the binary complexes of 2,6-difluorophenylacetylene with the four amines following resonant two-photon ionization can be explained on the basis of the intermolecular coulombic decay process.

Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes.

The red-shifts in the acetylenic C-H stretching vibration of C-H∙∙∙X (X = O, N) hydrogen-bonded complexes increase with an increase in the basicity of the Lewis base. Analysis of various components of stabilization energy suggests that the observed red-shifts are correlated with the electrostatic component of the stabilization energy, while the dispersion modulates the stabilization energy.

Multiphoton imaging of the monosachharide induced formation of fluorescent advanced glycation end products in tissues.

We studied the in vitro rate of fluorescent advanced glycation end products (fAGEs) formation with multiphoton microscopy in different porcine tissues (aorta, cornea, kidney, dermis, and tendon). These tissues were treated with d-glucose, d-galactose, and d-fructose, three primary monosaccharides found in human diets. We found that the use of d-fructose resulted in the highest glycation rate, followed by d-galactose and then d-glucose. Moreover, compared to non-collagen tissue constituents such as elastic fibers and cells, the rate of tissue glycation was consistently higher in collagen, suggesting that collagen is a more sensitive target for fAGE formation. However, we also found that collagen in different tissues exhibits different rates of fAGE formation, with slower rates observed in tightly packed tissues such as cornea and tendon. Our study suggests that for fAGE to be developed into a long-term glycemic biomarker, loosely organized collagen tissues located in the proximity of vasculature may be the best targets.

Binary complexes of ammonia with phenylacetylenes: a combined experimental and computational approach to explore multiple minima on intermolecular potentials.

The hydrogen-bonded complexes of phenylacetylene, 4-fluorophenylacetylene, 2-fluorophenylacetylene, and 2,6-difluorophenylacetylene with ammonia are investigated using IR-UV double resonance spectroscopy in combination with high-level ab initio calculations at the CCSD(T)/CBS level of theory. The C-H···N hydrogen-bonded complex, which involves an interaction of ammonia with the acetylenic CH group is the global minimum and is observed in all four cases investigated. In addition, phenylacetylene and 4-fluorophenylacetylene form a quasi-planar cyclic complexes with ammonia incorporating N-H···π and C-H···N hydrogen bonds, wherein the π-electron density of the acetylenic C≡C bond acts as an acceptor to the N-H group of ammonia. A third ammonia complex is observed for 4-fluorophenylacetylene in which ammonia interacts with the fluorine atom once again, leading to the formation of a quasi-planar cyclic complex. The substitution of the fluorine atom on the phenyl ring of phenylacetylene modulates the intermolecular potentials, which are dependent on the position of the substitution.

Imaging a Resonance-Dominant Polyatomic Reaction: F + CH3D → CH3(ν2 = 2) + DF(ν).

The title reaction was studied in a crossed-beam scattering experiment at the collisional energy ( Ec) ranging from 0.46 to 4.53 kcal mol-1. Using a time-sliced velocity-imaging technique, both the pair-correlated integral and differential cross sections were measured. On the basis of the observed structures in state-specific excitation functions and the patterns in the Ec evolution of product angular distributions, we inferred that the title reaction proceeds predominantly via a resonance-mediated pathway, in contrast to the previous findings in the isotopically analogous reactions where the alternative direct abstraction pathway often dominates the reactivity. Despite the complexity of numerous scattering resonances involved in this six-atom reaction, extending our understanding of the isolated resonance in the analogous benchmark F + HD (H2) reaction enables us to propose plausible mechanistic origins for the formation as well as the decay of the complicated overlapped resonances.