Correlated Product Distributions in the Photodissociation of à State NO-CH4 and NO-N2 van der Waals Complexes.

This paper reports correlated product distributions for dissociation of the van der Waals complexes NO-CH4 and NO-N2 on their à state surfaces, providing detailed data sets against which calculations can be benchmarked. NO-CH4 dissociation strongly favors small changes in the CH4 angular momentum, with ΔJ = 0 and 1 providing the bulk of the products. Conversely, the associated NO products show little constraint in terms of the rotational angular momentum transfer, with the full range of energetically accessible angular momentum states populated, although the distributions show minima. The lack of angular momentum transfer to methane accompanied by broad, structured, angular momentum transfer to NO gives the NO-CH4 dissociation some qualitative similarities to NO-Rg complex dissociation. In contrast, for NO-N2, the cluster of highest probability products corresponds to high N2 angular momentum and low NO angular momentum, with a sharp drop in the probability for populating the highest energetically accessible J states. For both the NO and N2 products, there appears to be a constraint limiting angular momentum transfer at the highest energetically accessible rotational states. Both complexes show product distributions that include a component attributed to excitation from warm complexes, which provides insight into their internal energies. Interestingly, for NO-N2, the 44,475 cm-1 photolysis translational energy release distribution for N = 8 extends to energies beyond those accessible from the highest bound X̃ states. This indicates either that there are long-lived (>100 µs) states above the X̃ state binding energy or that there is another mechanism that also contributes to this distribution.

Strong Torsion-Vibration Interaction in N-Methylpyrrole Observed by Far-Infrared Spectroscopy.

An interaction between methyl torsion and the low-lying out-of-plane methyl wag vibration has been observed in toluene, p-fluorotoluene, and m-fluorotoluene, contravening the traditional assumption used when analyzing spectra that methyl torsion can be treated independently of the small-amplitude vibrations. When a methyl group is attached to a planar frame, out-of-plane methyl wag vibrations always occur, and hence this type of interaction between methyl torsion and vibration is potentially extensive. To probe whether this coupling occurs beyond toluene and its derivatives, we have studied the far-infrared absorption band for the out-of-plane methyl wagging mode in N-methylpyrrole. The torsional sequence structure reveals a particularly strong torsion-vibration interaction. Spectral simulations yield a torsion-vibration coupling matrix element of 34.0 cm-1, over twice the value for toluene. The large torsion-vibration coupling constant implies that there is a significant tilting of the methyl group out of plane. Quantum chemistry calculations reveal a much larger out-of-plane methyl tilt angle in N-methylpyrrole compared to toluene, qualitatively consistent with this expectation. This is the first nontoluene derivative for which this type of torsion-vibration interaction has been reported and shows that the effect extends beyond toluenes. When present, this interaction links small-amplitude vibrations to the methyl torsion, providing a mechanism to bring the increased density of states into play and accelerate the rate of intramolecular vibrational energy redistribution.

Torsion-vibration interactions determined from (far) infrared spectra.

Observations of the torsional and low-lying vibrational-torsional states of toluene, p-fluorotoluene, and m-fluorotoluene using the technique of two dimensional laser induced fluorescence (2D-LIF) have revealed interactions between the methyl torsion and low frequency out-of-plane methyl wagging vibration. These interactions can change the values of constants extracted from the analysis of rotational spectra, which usually assume that the large amplitude torsional motion can be treated independent of the small amplitude vibrations. Since out-of-plane methyl wagging modes will be present whenever a methyl group is attached to a planar frame, this type of torsion-vibration interaction is potentially widespread; it is thus important to establish the extent and strength of this type of interaction. 2D-LIF is limited to molecules that fluoresce from excited electronic states, and to explore interactions between torsion and methyl wagging vibrations in a wide range of molecules necessitates developing alternative experimental approaches. Infrared absorption spectroscopy is one such approach. It is shown that for the low torsional barrier case, the torsional sequence bands accompanying the out-of-plane methyl wagging transition provide a sensitive probe of the interaction. As an illustration, the far infrared absorption spectrum of toluene in the region of the M20 band (∼205 cm-1) is presented and analyzed. The torsional sequence structure provides insight into the higher torsional states (up to m = 7) in the ground vibrational state and M20. An analysis of these bands enables the torsion-vibration coupling and torsional constants to be extracted. A general method to analyze such spectra is presented.

Continuous flow vortex fluidic-mediated exfoliation and fragmentation of two-dimensional MXene.

MXene (Ti2CT x ) is exfoliated in a vortex fluidic device (VFD), as a thin film microfluidic platform, under continuous flow conditions, down to ca 3 nm thin multi-layered two-dimensional (2D) material, as determined using AFM. The optimized process, under an inert atmosphere of nitrogen to avoid oxidation of the material, was established by systematically exploring the operating parameters of the VFD, along with the concentration of the dispersed starting material and the choice of solvent, which was a 1 : 1 mixture of isopropyl alcohol and water. There is also some fragmentation of the 2D material into nanoparticles ca 68 nm in diameter.

Continuous Flow Copper Laser Ablation Synthesis of Copper(I and II) Oxide Nanoparticles in Water.

Copper(I) oxide (Cu2O) nanoparticles (NPs) are selectively prepared in high yields under continuous flow in a vortex fluidic device (VFD), involving irradiation of a copper rod using a pulsed laser operating at 1064 nm and 600 mJ. The plasma plume generated inside a glass tube (20 mm O.D.), which is rapidly rotating (7.5 k rpm), reacts with the enclosed air in the microfluidic platform, with then high mass transfer of material into the dynamic thin film of water passing up the tube. The average size of the generated Cu2ONPs is 14 nm, and they are converted to copper(II) oxide (CuO) nanoparticles with an average diameter of 11 nm by heating the as-prepared solution of Cu2ONPs in air at 50 °C for 10 h.

A strong interaction between torsion and vibration in S0 and S1m-fluorotoluene.

We report results of a two dimensional laser induced fluorescence study of torsional states, low frequency vibrations, and combinations of torsion with low frequency vibration in m-fluorotoluene up to 560 cm-1 in S0 and 350 cm-1 in S1. Evidence is presented for interactions between torsion and low frequency vibrations in both S0 and S1, demonstrating that the coupling of torsion and vibration observed previously in toluene and p-fluorotoluene extends to a molecule with a threefold torsional barrier. This barrier is low in S0 (20 cm-1) and modest in S1 (116 cm-1). The methyl torsion-vibration interaction is much larger for the mode involving out-of-plane wagging of the methyl group with respect to the planar frame compared with the analogous out-of-plane fluorine atom motion. Methyl group out-of-plane modes were found to be most important for torsion-vibration interactions in toluene and p-fluorotoluene, and the evidence is accumulating that this motion is fundamental in torsion-vibration interactions. Fits of the experimental band positions yield torsion-vibration coupling constants, torsional potential terms (V3 and V6), and rotational constants (F) for the methyl torsion in S0 and S1. The inclusion of torsion-vibration coupling primarily affects V6 and F: |V6| is reduced and F increased, as was seen previously for the G12 molecules, toluene and p-fluorotoluene. The torsional barrier height does not appear to influence the magnitude of the torsion-vibration interaction: the coupling constants for the out-of-plane CH3 wag mode are almost the same in S0 and S1 (15.5 cm-1 and 14.0 cm-1, respectively).

Inverted vortex fluidic exfoliation and scrolling of hexagonal-boron nitride.

Exfoliation or scrolling of hexagonal boron nitride (h-BN) occurs in a vortex fluidic device (VFD) operating under continuous flow, with a tilt angle of -45° relative to the horizontal position. This new VFD processing strategy is effective in avoiding the build-up of material that occurs when the device is operated using the conventional tilt angle of +45°, where the h-BN precursor and scrolls are centrifugally held against the wall of the tube. At a tilt angle of -45° the downward flow aided by gravity facilitates material exiting the tube with the exfoliation of h-BN and formation of h-BN scrolls then optimized by systematically varying the other VFD operating parameters, including flow rate and rotational speed, along with concentration of h-BN and the choice of solvent. Water was the most effective solvent, which enhances the green chemistry metrics of the processing.

Dynamic thin film mediated slicing of boron nitride nanotubes.

A method has been developed to slice boron nitride nanotubes BNNTs under continuous flow in a vortex fluidic device (VFD), along with a method to partially purify the as received BNNT containing material. The latter involves heating the BNNTs to 600 °C followed by dispersing in a 1 : 3 isopropyl alcohol (IPA) and water mixture at 100 °C. The VFD mediated slicing of the BNNTs comprises irradiating the rapidly rotating glass tube (20 mm OD) with a pulsed Nd:YAG laser. Systematically exploring the operating parameter space of the VFD established slicing of ca. 200 µm long purified BNNTs down to 340 nm to 400 nm, in ca. 53% yield, in a 1 : 1 mixture of IPA and water, in the absence of reagents/harsh chemicals, at a flow rate of 0.45 mL min-1, a concentration of 0.1 mg mL-1 BNNTs and an 8.5k rpm rotational speed, with the pulsed laser operating at 1064 nm and 250 mJ per pulse.

Pervasive interactions between methyl torsion and low frequency vibrations in S0 and S1p-fluorotoluene.

We report two dimensional laser induced fluorescence spectral images exploring the lower torsion-vibration manifolds in S0 (E < 560 cm-1) and S1 (E < 420 cm-1) p-fluorotoluene. Analysis of the images reveals strong torsion-vibration interactions and provides an extensive set of torsion-vibration state energies in both electronic states (estimated uncertainty ±0.2 cm-1), which are fit to determine key constants including barrier heights, torsional constants, and torsion-vibration interaction constants. The dominant interactions in both electronic states are between methyl torsion (internal rotation) and the lowest frequency out-of-plane modes, D20 and D19, both of which involve a methyl wagging motion. This is the second aromatic (following toluene) for which a significant interaction between torsion and methyl out-of-plane wagging vibrations has been quantified. Given the generic nature of this motion in substituted toluenes and similar molecules, this mechanism for torsion-vibration coupling may be common in these types of molecules. The inclusion of torsion-vibration coupling affects key molecular constants such as barrier heights and torsional (and rotational) constants, and the possibility of such an interaction should thus be considered in spectral analyses when determining parameters in these types of molecules. p-Fluorotoluene is the first molecule in which the role of methyl torsion in promoting intramolecular vibrational energy redistribution (IVR) was established and the observed torsion-vibration coupling provides one conduit for the state mixing that is a precursor to IVR, as originally proposed by Moss et al. [J. Chem. Phys. 86, 51 (1987)].

A "circularisation" method to repair deformations and determine the centre of velocity map images.

A problem besetting the analysis of velocity map images, particularly those of photoelectrons, is the presence of distortions that cause the features in the image to deviate from circularity, leading to a loss of resolution in the spectrum extracted. A method is presented to repair such distortions based on fitting the angular behaviour of each of the ring structures to a trigonometric expansion. The repair function allows the intensity at any value of radius and angle to be mapped to a new position that removes the distortion and returns the features to circular. While the method relies on the analysis of the structure in an image, it could also be applied to determine the "repair function" using a calibration image (or series of images) for the experiment. Once the image has been circularised it can be processed by any of the approaches that have been developed for that purpose. The analysis also enables the image centre to be determined with high accuracy. The fitting method utilises an inverse Abel transformation of the image in polar coordinates as a means to reshape the image into a series of spectral features in order to determine the radial position of features at each angle. Although the velocity distribution is not in general spherically symmetric and so this is not a mathematically correct means to extract the velocity distribution, the feature positions are accurately reproduced in the resulting spectrum while the intensity and anisotropy parameters can be remarkably close to those obtained using the proper inverse Abel transformation of the image.

First spectroscopic observation of gold(i) butadiynylide: Photodetachment velocity map imaging of the AuC4H anion.

The velocity map imaging technique was used in the investigation of gold(i) butadiynylide, AuC4H(-), with images recorded at two excitation wavelengths. The resultant photodetachment spectra show a well defined vibrational progression in the neutral with an energy spacing of 343 ± 3 cm(-1). The adiabatic electron affinity was determined to be 1.775 ± 0.005 eV and assigned to the X(1)Σ(+)←X(2)Σ(+) transition between the anionic and neutral ground states. Franck-Condon simulations performed on density functional theory optimized geometries assisted the assignment of linear geometries to the neutral and anion and the observed vibrational progression to that of the Au-C4H stretch.

Fluid dynamic lateral slicing of high tensile strength carbon nanotubes.

Lateral slicing of micron length carbon nanotubes (CNTs) is effective on laser irradiation of the materials suspended within dynamic liquid thin films in a microfluidic vortex fluidic device (VFD). The method produces sliced CNTs with minimal defects in the absence of any chemical stabilizers, having broad length distributions centred at ca 190, 160 nm and 171 nm for single, double and multi walled CNTs respectively, as established using atomic force microscopy and supported by small angle neutron scattering solution data. Molecular dynamics simulations on a bent single walled carbon nanotube (SWCNT) with a radius of curvature of order 10 nm results in tearing across the tube upon heating, highlighting the role of shear forces which bend the tube forming strained bonds which are ruptured by the laser irradiation. CNT slicing occurs with the VFD operating in both the confined mode for a finite volume of liquid and continuous flow for scalability purposes.

Rotational and angular distributions of NO products from NO-Rg (Rg = He, Ne, Ar) complex photodissociation.

We present the results of an investigation into the rotational and angular distributions of the NO à state fragment following photodissociation of the NO-He, NO-Ne, and NO-Ar van der Waals complexes excited via the à ← X̃ transition. For each complex, the dissociation is probed for several values of Ea, the available energy above the dissociation threshold. For NO-He, the Ea values probed were 59, 172, and 273 cm(-1); for NO-Ne they were 50 and 166 cm(-1); and for NO-Ar they were 44, 94, 194, and 423 cm(-1). The NO à state rotational distributions arising from NO-He are cold, with most products in low angular momentum states. NO-Ne leads to broader NO rotational distributions but they do not extend to the maximum possible given the energy available. In the case of NO-Ar, the distributions extend to the maximum allowed at that energy and show the unusual shapes associated with the rotational rainbow effect reported in previous studies. This is the only complex for which a rotational rainbow effect is observed at the chosen Ea values. Product angular distributions have also been measured for the NO à photodissociation product for the three complexes. NO-He produces nearly isotropic fragments, but the anisotropy parameter, ß, for NO-Ne and NO-Ar photofragments shows a surprising change in sign from negative to positive as Ea increases within the unstructured excitation profile. Franck-Condon selection of a broader distribution of geometries including more linear geometries at lower excitation energies and more T-shaped geometries at higher energies can account for the changing recoil anisotropy. Two-dimensional wavepacket calculations are reported to model the rotational state distributions and the bound-continuum absorption spectra.

Torsion-vibration coupling in S1 toluene: Implications for IVR, the torsional barrier height, and rotational constants.

We have examined the S1←S0 transition of toluene in the region from the 0(0)(0) band to ∼210 cm(-1) above it. The spectrum reveals methyl rotor levels of 0(0) toluene up to m = 6 and of the lowest frequency vibration, 20(1), up to m = 4. The rotor levels of both 20(1) and 0(0) are perturbed by torsion-vibration coupling. The inclusion of torsion-vibration coupling leads to the S1 torsional barrier, V6, being revised from -26.376 cm(-1) to -5.59 cm(-1). The torsion-vibration coupling constant is determined to be 21.1 cm(-1). This situation is the S1 analogue of that recently reported for S0 toluene [Gascooke et al., J. Chem. Phys. 142, 024315 (2015)]. Torsion-vibration coupling alters both the rotor band positions and the rotational contours, which particularly affects the rotational constants associated with motion around the a-axis, about which the methyl group rotates. Every vibrational state (indicated generically by X) will be involved in the corresponding X - X20(1) torsion-vibration coupling; so, this interaction permeates the vib-rotor manifold, providing a mechanism to enhance intramolecular vibrational energy redistribution.

Direct observation of methyl rotor and vib-rotor states of S0 toluene: a revised torsional barrier due to torsion-vibration coupling.

We report a two dimensional, laser induced fluorescence study of the lowest 345 cm(-1) region of S0 toluene. Methyl rotor levels of 00 up to m = 6 and of 201 up to m = 4 are observed. The rotor levels of 00 and 201 have quite different energy spacings that are well fit by a model that includes strong torsion-vibration coupling between them. The model requires that the rotor barrier height be revised from -4.84 cm(-1) (methyl hydrogens in a staggered conformation) to +1.57 cm(-1) (eclipsed conformation). However, the 3a2″ state lies below the 3a1″ state as expected for a staggered conformation due to energy shifts associated with the torsion-vibration coupling. It is shown that the rotor wave-functions exhibit little localization at the torsional energy minima. The variation in the m = 0 wavefunction probability distribution with torsional angle is shown to be very similar for the previously accepted negative V6 value and the torsion-vibration coupling model as this coupling shifts the phase of the wavefunction by 30° compared with its phase for V6 alone. The presence of a strong Δυ = ± 1 torsion-vibration coupling involving the lowest frequency vibrational mode provides a potential pathway for rapid intramolecular vibrational energy redistribution at higher energies.

Spectroscopic observation of gold-dicarbide: photodetachment and velocity map imaging of the AuC2 anion.

Photoelectron spectra following photodetachment of the gold dicarbide anion, AuC2(-), have been recorded using the velocity map imaging technique at several excitation wavelengths. The binding energy spectra show well-defined vibrational structure which, with the aid of computational calculations and Franck-Condon simulations, was assigned to a progression in the Au-C stretching mode, ν3. The experimental data indicate that the features in the spectrum correspond to a (2)A' ← (3)A' transition, involving states which we calculate to have bond angles ~147° but with a low barrier to linearity.

Methyl rotor dependent vibrational interactions in toluene.

The methyl rotor dependence of a three state Fermi resonance in S1 toluene at ∼460 cm(-1) has been investigated using two-dimensional laser induced fluorescence. An earlier time-resolved study has shown the Fermi resonance levels to have different energy spacings at the two lowest methyl rotor states, m = 0 and 1 [J. A. Davies, A. M. Green, and K. L. Reid, Phys. Chem. Chem. Phys. 12, 9872 (2010)]. The overlapped m = 0 and 1 spectral features have been separated to provide direct spectral evidence for the m dependence of the resonance. The resonance has been probed at m = 3a(") 1 for the first time and found to be absent, providing further evidence for a large change in the interaction with m. Deperturbing the resonance at m = 0 and 1 reveals that the m dependence arises through differences in the separations of the "zero-order," locally coupled states. It is shown that this is the result of the local "zero-order" states being perturbed by long-range torsion-vibration coupling that shifts their energy by small amounts. The m dependence of the shifts arises from the Δm = ±3n (n = 1, 2, ...) coupling selection rule associated with torsion-rotation coupling in combination with the m(2) scaling of the rotor energies, which changes the ΔE for the interaction for each m. There is also an increase in the number of states that can couple to m = 1 compared with m = 0. Consideration of the magnitude of reported torsion-rotation coupling constants suggests that this effect is likely to be pervasive in molecules with methyl rotors.

The toluene-Ar complex: S0 and S1 van der Waals modes, changes to methyl rotation, and torsion-van der Waals vibration coupling.

The methyl rotor and van der Waals vibrational levels in the S1 and S0 states of toluene-Ar have been investigated by the technique of two-dimensional laser induced fluorescence (2D-LIF). The S0 van der Waals and methyl rotor levels are reported for the first time, while improved S1 values are presented. The correlations seen in the 2D-LIF images between the S0 and S1 states lead to a reassignment of key features in the S1 ← S0 excitation spectrum. This reassignment reveals that there are significant changes in the methyl rotor levels in the complex compared with those in bare toluene, particularly at low m. The observed rotor energies are explained by the introduction of a three-fold, V3, term in the torsion potential (this term is zero in toluene) and a reduction in the height of the six-fold, V6, barriers in S0 and S1 from their values in bare toluene. The V3 term is larger in magnitude than the V6 term in both S0 and S1. The constants determined are ∣V3(S1)∣ = 33.4 ± 1.0 cm(-1), ∣V3(S0)∣ = 20.0 ± 1.0 cm(-1), V6(S1) = -10.7 ± 1.0 cm(-1), and V6(S0) = -1.7 ± 1.0 cm(-1). The methyl rotor is also found to couple with van der Waals vibration; specifically, the m(") = 2 rotor state couples with the combination level involving one quantum of the long axis bend and m(") = 1. The coupling constant is determined to be 1.9 cm(-1), which is small compared with the values typically reported for torsion-vibration coupling involving ring modes.

Intermolecular vibrations of fluorobenzene-Ar up to 130 cm(-1) in the ground electronic state.

Sixteen intermolecular vibrational levels of the S(0) state of the fluorobenzene-Ar van der Waals complex have been observed using dispersed fluorescence. The levels range up to ~130 cm(-1) in vibrational energy. The vibrational energies have been modelled using a complete set of harmonic and quartic anharmonic constants and a cubic anharmonic coupling between the stretch and long axis bend overtone that becomes near ubiquitous at higher energies. The constants predict the observed band positions with a root mean square deviation of 0.04 cm(-1). The set of vibrational levels predicted by the constants, which includes unobserved bands, has been compared with the predictions of ab initio calculations, which include all vibrational levels up to 70-75 cm(-1). There are small differences in energy, particularly above 60 cm(-1), however, the main differences are in the assignments and are largely due to the limitations of assigning the ab initio wavefunctions to a simple stretch, bend, or combination when the states are mixed by the cubic anharmonic coupling. The availability of these experimental data presents an opportunity to extend ab initio calculations to higher vibrational energies to provide an assessment of the accuracy of the calculated potential surface away from the minimum. The intermolecular modes of the fluorobenzene-Ar(2) trimer complex have also been investigated by dispersed fluorescence. The dominant structure is a pair of bands with a ~35 cm(-1) displacement from the origin band. Based on the set of vibrational modes calculated from the fluorobenzene-Ar frequencies, they are assigned to a Fermi resonance between the symmetric stretch and symmetric short axis bend overtone. The analysis of this resonance provides a measurement of the coupling strength between the stretch and short axis bend overtone in the dimer, an interaction that is not directly observed. The coupling matrix elements determined for the fluorobenzene-Ar stretch-long axis bend overtone and stretch-short axis bend overtone couplings are remarkably similar (3.8 cm(-1) cf. 3.2 cm(-1)). Several weak features seen in the fluorobenzene-Ar(2) spectrum have also been assigned.

Two-dimensional laser induced fluorescence spectroscopy of van der Waals complexes: fluorobenzene-Ar(n) (n = 1,2).

The technique of two-dimensional laser induced fluorescence (2D-LIF) spectroscopy has been used to observe the van der Waals complexes fluorobenzene-Ar and fluorobenzene-Ar(2) in the region of their S(1)-S(0) electronic origins. The 2D-LIF spectral images reveal a number of features assigned to the van der Waals vibrations in S(0) and S(1). An advantage of 2D-LIF spectroscopy is that the LIF spectrum associated with a particular species may be extracted from an image. This is illustrated for fluorobenzene-Ar. The S(1) van der Waals modes observed in this spectrum are consistent with previous observations using mass resolved resonance enhanced multiphoton ionisation techniques. For S(0), the two bending modes previously observed using a Raman technique were observed along with three new levels. These agree exceptionally well with ab initio calculations. The Fermi resonance between the stretch and bend overtone has been analysed in both the S(0) and S(1) states, revealing that the coupling is stronger in S(0) than in S(1). For fluorobenzene-Ar(2) the 2D-LIF spectral image reveals the S(0) symmetric stretch van der Waals vibration to be 35.0 cm(-1), closely matching the value predicted based on the fluorobenzene-Ar van der Waals stretch frequency. Rotational band contour analysis has been performed on the fluorobenzene-Ar 0(0)(0) transition to yield a set of S(1) rotational constants A' = 0.05871 ± 0.00014 cm(-1), B' = 0.03803 ± 0.00010 cm(-1), and C' = 0.03103 ± 0.00003 cm(-1). The rotational constants imply that in the S(1) 0(0) level the Ar is on average 3.488 Å from the fluorobenzene centre of mass and displaced from it towards the centre of the ring at an angle of ~6° to the normal. The rotational contour for fluorobenzene-Ar(2) was predicted using rotational constants calculated on the basis of the fluorobenzene-Ar geometry and compared with the experimental contour. The comparison is poor which, while due in part to expected saturation effects, suggests the presence of another band lying beneath the contour.