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Photoelectron angular distributions (PADs) produced from the photoionization of chiral molecules using elliptically polarized light exhibit a forward/backward asymmetry with respect to the optical propagation direction. By recording these distributions using the velocity-map imaging (VMI) technique, the resulting photoelectron elliptical dichroism (PEELD) has previously been demonstrated as a promising spectroscopic tool for studying chiral molecules in the gas phase. The use of elliptically polarized laser pulses, however, produces PADs (and consequently, PEELD distributions) that do not exhibit cylindrical symmetry about the propagation axis. This leads to significant limitations and challenges when employing conventional VMI acquisition and data processing strategies. Using novel photoelectron image analysis methods based around Hankel transform reconstruction tomography and machine learning, however, we have quantified—for the first time—significant symmetry-breaking contributions to PEELD signals that are of a comparable magnitude to the symmetric terms in the multiphoton ionization of (1R,4R)-(+)- and (1S,4S)-(−)-camphor. This contradicts any assumptions that symmetry-breaking can be ignored when reconstructing VMI data. Furthermore, these same symmetry-breaking terms are expected to appear in any experiment where circular and linear laser fields are used together. This ionization scheme is particularly relevant for investigating dynamics in chiral molecules, but it is not limited to them. Developing a full understanding of these terms and the role they play in the photoionization of chiral molecules is of clear importance if the potential of PEELD and related effects for future practical applications is to be fully realized. [ABSTRACT FROM AUTHOR]

Examples of extracting meaningful information from image projection data using tomographic reconstruction techniques can be found in many areas of science. Within the photochemical dynamics community, tomography allows for complete three-dimensional (3D) charged particle momentum distributions to be reconstructed following a photodissociation or photoionization event. This permits highly differential velocity- and angle-resolved measurements to be made simultaneously. However, the generalized tomographic reconstruction strategies typically adopted for use with photochemical imaging—based around the Fourier-slice theorem and filtered back-projection algorithms—are not optimized for these specific types of problems. Here, we discuss pre-existing alternative strategies—namely, the simultaneous iterative reconstruction technique and Hankel Transform Reconstruction (HTR)—and introduce them in the context of velocity-map imaging applications. We demonstrate the clear advantages they afford, and how they can perform considerably better than approaches commonly adopted at present. Most notably, with HTR we can set a bound on the minimum number of projections required to reliably reconstruct 3D photoproduct distributions. This bound is significantly lower than what is currently accepted and will help make tomographic imaging far more accessible and efficient for many experimentalists working in the field of photochemical dynamics. [ABSTRACT FROM AUTHOR]

A new method for the fully generalized reconstruction of three-dimensional (3D) photoproduct distributions from velocity-map imaging (VMI) projection data is presented. This approach, dubbed Fourier–Hankel–Abel Nyquist-limited TOMography (FHANTOM), builds on recent previous work in tomographic image reconstruction [C. Sparling and D. Townsend, J. Chem. Phys. 157, 114201 (2022)] and takes advantage of the fact that the distributions produced in typical VMI experiments can be simply described as a sum over a small number of spherical harmonic functions. Knowing the solution is constrained in this way dramatically simplifies the reconstruction process and leads to a considerable reduction in the number of projections required for robust tomographic analysis. Our new method significantly extends basis set expansion approaches previously developed for the reconstruction of photoproduct distributions possessing an axis of cylindrical symmetry. FHANTOM, however, can be applied generally to any distribution—cylindrically symmetric or otherwise—that can be suitably described by an expansion in spherical harmonics. Using both simulated and real experimental data, this new approach is tested and benchmarked against other tomographic reconstruction strategies. In particular, the reconstruction of photoelectron angular distributions recorded in a strong-field ionization regime—marked by their extensive expansion in terms of spherical harmonics—serves as a key test of the FHANTOM methodology. With the increasing use of exotic optical polarization geometries in photoionization experiments, it is anticipated that FHANTOM and related reconstruction techniques will provide an easily accessible and relatively low-cost alternative to more advanced 3D-VMI spectrometers. [ABSTRACT FROM AUTHOR]

Time-resolved photoelectron spectroscopy in combination with ab initio quantum chemistry calculations was used to study ultrafast excited state dynamics in formamide (FOR), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA) following 160 nm excitation. The particular focus was on internal conversion processes within the excited state Rydberg manifold and on how this behavior in amides compared with previous observations in small amines. All three amides exhibited extremely rapid (<100 fs) evolution from the Franck–Condon region. We argue that this is then followed by dissociation. Our calculations indicate subtle differences in how the excited state dynamics are mediated in DMA/DMF as compared to FOR. We suggest that future studies employing longer pump laser wavelengths will be useful for discerning these differences. [ABSTRACT FROM AUTHOR]

Wavelength-dependent measurements of the RNA base uracil, undertaken with nanosecond ultraviolet laser pulses, have previously identified a fragment at m/z = 84 (corresponding to the C3H4N2O+ ion) at excitation wavelengths ≤232 nm. This has been interpreted as a possible signature of a theoretically predicted ultrafast ring-opening occurring on a neutral excited state potential energy surface. To further investigate the dynamics of this mechanism, and also the non-adiabatic dynamics operating more generally in uracil, we have used a newly built ultra-high vacuum spectrometer incorporating a laser-based thermal desorption source to perform time-resolved ion-yield measurements at pump wavelengths of 267 nm, 220 nm, and 200 nm. We also report complementary data obtained for the related species 2-thiouracil following 267 nm excitation. Where direct comparisons can be made (267 nm), our findings are in good agreement with the previously reported measurements conducted on these systems using cold molecular beams, demonstrating that the role of initial internal energy on the excited state dynamics is negligible. Our 220 nm and 200 nm data also represent the first reported ultrafast study of uracil at pump wavelengths <250 nm, revealing extremely rapid (<200 fs) relaxation of the bright S3(1ππ*) state. These measurements do not, however, provide any evidence for the appearance of the m/z = 84 fragment within the first few hundred picoseconds following excitation. This key finding indicates that the detection of this specific species in previous nanosecond work is not directly related to an ultrafast ring-opening process. An alternative excited state process, operating on a more extended time scale, remains an open possibility. [ABSTRACT FROM AUTHOR]

Many charged particle imaging measurements rely on the inverse Abel transform (or related methods) to reconstruct three-dimensional (3D) photoproduct distributions from a single two-dimensional (2D) projection image. This technique allows for both energy- and angle-resolved information to be recorded in a relatively inexpensive experimental setup, and its use is now widespread within the field of photochemical dynamics. There are restrictions, however, as cylindrical symmetry constraints on the overall form of the distribution mean that it can only be used with a limited range of laser polarization geometries. The more general problem of reconstructing arbitrary 3D distributions from a single 2D projection remains open. Here, we demonstrate how artificial neural networks can be used as a replacement for the inverse Abel transform and—more importantly—how they can be used to directly "reinflate" 2D projections into their original 3D distributions, even in cases where no cylindrical symmetry is present. This is subject to the simulation of appropriate training data based on known analytical expressions describing the general functional form of the overall anisotropy. Using both simulated and real experimental data, we show how our arbitrary image reinflation (AIR) neural network can be utilized for a range of different examples, potentially offering a simple and flexible alternative to more expensive and complicated 3D imaging techniques. [ABSTRACT FROM AUTHOR]

We present a crossed molecular beam scattering study, using velocity-map ion-imaging detection, of state-to-state rotational energy transfer for NO(A²Σ+) in collisions with the kinematically identical colliders He and D2. We report differential cross sections and angle-resolved rotational angular momentum polarization moments for transfer of NO(A, v = 0, N = 0, j = 0.5) to NO(A, v = 0, N' = 3, 5-12) in collisions with He and D2 at respective average collision energies of 670 cm-1 and 663 cm-1. Quantum scattering calculations on a literature ab initio potential energy surface for NO(A)-He [J. Kłos et al., J. Chem. Phys. 129, 244303 (2008)] yield near-quantitative agreement with the experimental differential scattering cross sections and good agreement with the rotational polarization moments. This confirms that the Kłos et al. potential is accurate within the experimental collisional energy range. Comparison of the experimental results for NO(A) + D2 and He collisions provides information on the hitherto unknown NO(A)-D2 potential energy surface. The similarities in the measured scattering dynamics of NO(A) imply that the general form of the NO(A)-D2 potential must be similar to that calculated for NO(A)-He. A consistent trend for the rotational rainbow maximum in the differential cross sections for NO(A) + D2 to peak at more forward angles than those for NO(A) + He is consistent with the NO(A)-D2 potential being more anisotropic with respect to NO(A) orientation. No evidence is found in the experimental measurements for coincident rotational excitation of the D2, consistent with the potential having low anisotropy with respect to D2. The NO(A) + He polarization moments deviate systematically from the predictions of a hard-shell, kinematic-apse scattering model, with larger deviations as N' increases, which we attribute to the shallow gradient of the anisotropic repulsive NO(A)-He potential energy surface. [ABSTRACT FROM AUTHOR]

We present the implementation of a new crossed-molecular beam, velocity-map ion-imaging apparatus, optimized for collisions of electronically excited molecules. We have applied this apparatus to rotational energy transfer in NO(A²Σ+, v = 0, N = 0, j = 0.5) + Ar collisions, at an average energy of 525 cm-1. We report differential cross sections for scattering into NO(A²Σ+, v = 0, N' = 3, 5, 6, 7, 8, and 9), together with quantum scattering calculations of the differential cross sections and angle dependent rotational alignment. The differential cross sections show dramatic forward scattered peaks, together with oscillatory behavior at larger scattering angles, while the rotational alignment moments are also found to oscillate as a function of scattering angle. In general, the quantum scattering calculations are found to agree well with experiment, reproducing the forward scattering and oscillatory behavior at larger scattering angles. Analysis of the quantum scattering calculations as a function of total rotational angular momentum indicates that the forward scattering peak originates from the attractive minimum in the potential energy surface at the N-end of the NO. Deviations in the quantum scattering predictions from the experimental results, for scattering at angles greater than 10°, are observed to be more significant for scattering to odd final N'. We suggest that this represents inaccuracies in the potential energy surface, and in particular in its representation of the difference between the N- and O-ends of the molecule, as given by the odd-order Legendre moments of the surface. [ABSTRACT FROM AUTHOR]

Time-resolved photoelectron imaging was used to investigate the electronic relaxation dynamics of gas-phase aniline, N, N-dimethylaniline, and 3,5-dimethylaniline following ultraviolet excitation at 250 nm. Our analysis was supported by ab initio coupled-cluster calculations evaluating excited state energies and (in aniline) the evolution of a range of excited state physical properties as a function of N-H bond extension. Due to a lack of consistency between several earlier studies undertaken in aniline, the specific aim of this present work was to gain new insight into the previously proposed non-adiabatic coupling interaction between the two lowest lying singlet excited states S1(ΠΠ*) and S2(3s/Πσ*). The methyl-substituted systems N, N-dimethylaniline and 3,5-dimethylaniline were included in order to obtain more detailed dynamical information about the key internal molecular coordinates that drive the S1(ΠΠ*)/S2(3s/Πσ*) coupling mechanism. Our findings suggest that in all three systems, both electronic states are directly populated during the initial excitation, with the S2(3s/Πσ*) state then potentially decaying via either direct dissociation along the N-X stretching coordinate (X = H or CH3) or internal conversion to the S1(ΠΠ*) state. In aniline and N, N-dimethylaniline, both pathways most likely compete in the depletion of S2(3s/Πσ*) state population. However, in 3,5-dimethylaniline, only the direct dissociation mechanism appears to be active. This is rationalized in terms of changes in the relative rates of the two decay pathways upon methylation of the aromatic ring system. [ABSTRACT FROM AUTHOR]

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (ππ*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1-2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (πσ*) state, which is dissociative along the O-H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement. [ABSTRACT FROM AUTHOR]

Time-resolved photoelectron spectroscopy was used to obtain new information about the dynamics of electronic relaxation in gas-phase indole and 5-hydroxyindole following UV excitation with femtosecond laser pulses centred at 249 nm and 273 nm. Our analysis of the data was supported by ab initio calculations at the coupled cluster and complete-active-space self-consistent-field levels. The optically bright 1La and 1Lb electronic states of 1ππ* character and spectroscopically dark and dissociative 1πσ* states were all found to play a role in the overall relaxation process. In both molecules we conclude that the initially excited 1La state decays non-adiabatically on a sub 100 fs timescale via two competing pathways, populating either the subsequently long-lived 1Lb state or the 1πσ* state localised along the N-H coordinate, which exhibits a lifetime on the order of 1 ps. In the case of 5-hydroxyindole, we conclude that the 1πσ* state localised along the O-H coordinate plays little or no role in the relaxation dynamics at the two excitation wavelengths studied. [ABSTRACT FROM AUTHOR]

The authors report time resolved photoelectron spectra of the 1B2(1Σu+) state of CS2 at pump wavelengths in the region of 200 nm. In contrast to previous studies, the authors find that the predissociation dynamics is not well described by a single exponential decay. Biexponential modeling of the authors’ data reveals a rapid decay pathway (τ<50 fs), in addition to a longer lived channel (τ∼350–650 fs) that displays a marked change in apparent lifetime when the polarization of the pump laser is rotated with respect to that of the probe. Since the initially populated 1B2(1Σu+) state may decay to form either S(1D) or S(3P) products (the latter produced via a spin-orbit induced crossing from a singlet to a triplet electronic surface), this lifetime observation may be rationalized in terms of changes in the relative ionization cross section of these singlet and triplet states of CS2 as a function of laser polarization geometry. The experimentally observed lifetime of the longer lived channel is therefore a superposition of these two pathways, both of which decay on very similar time scales. [ABSTRACT FROM AUTHOR]

The authors report time resolved photoelectron spectra of the 1B2(1Σu+) state of CS2 at pump wavelengths in the region of 200 nm. In contrast to previous studies, the authors find that the predissociation dynamics is not well described by a single exponential decay. Biexponential modeling of the authors’ data reveals a rapid decay pathway (τ<50 fs), in addition to a longer lived channel (τ∼350–650 fs) that displays a marked change in apparent lifetime when the polarization of the pump laser is rotated with respect to that of the probe. Since the initially populated 1B2(1Σu+) state may decay to form either S(1D) or S(3P) products (the latter produced via a spin-orbit induced crossing from a singlet to a triplet electronic surface), this lifetime observation may be rationalized in terms of changes in the relative ionization cross section of these singlet and triplet states of CS2 as a function of laser polarization geometry. The experimentally observed lifetime of the longer lived channel is therefore a superposition of these two pathways, both of which decay on very similar time scales. [ABSTRACT FROM AUTHOR]

We present a detailed experimental and theoretical investigation of formaldehyde photodissociation to H2 and CO following excitation to the 2141 and 2143 transitions in S1. The CO velocity distributions were obtained using dc slice imaging of single CO rotational states (v=0, jCO=5–45). These high-resolution measurements reveal the correlated internal state distribution in the H2 cofragments. The results show that rotationally hot CO (jCO∼45) is produced in conjunction with vibrationally “cold” H2 fragments (v=0–5): these products are formed through the well-known skewed transition state and described in detail in the accompanying paper. After excitation of formaldehyde above the threshold for the radical channel (H2CO→H+HCO) we also find formation of rotationally cold CO (jCO=5–28) correlated to highly vibrationally excited H2 (v=6–8). These products are formed through a novel mechanism that involves near dissociation followed by intramolecular H abstraction [D. Townsend et al., Science 306, 1158 (2004)], and that avoids the region of the transition state entirely. The dynamics of this “roaming” mechanism are the focus of this paper. The correlations between the vibrational states of H2 and rotational states of CO formed following excitation on the 2143 transition allow us to determine the relative contribution to molecular products from the roaming atom channel versus the conventional molecular channel. [ABSTRACT FROM AUTHOR]

We report a new variation of the velocity map ion imaging method that allows the central section of the photofragment ion cloud to be recorded exclusively. The relevant speed and angular distributions for a molecular photodissociation or scattering event may therefore be obtained without need to utilize inversion methods such as the inverse Abel transform. In contrast to the recently reported "slicing" technique of Kitsopoulos and co-workers [C. R. Gebhardt et al., Rev. Sci. Instrum. 72, 3848 (2001)], our method makes no use of grids or pulsed electric fields which can distort the photofragment cloud and therefore compromise the resolution of velocity mapping. We find that by operating a multilens velocity mapping assembly at low voltages, the ion cloud stretches in the acceleration region owing to the kinetic energy release in the fragments. Furthermore, this inherent stretching is sufficient to allow the central section of the distribution to be recorded exclusively by application of a narrow time gate (∼40 ns) to a position sensitive detector. We have performed extensive ion trajectory simulations to understand this "direct current (dc) slice imaging" technique, and experimentally we have applied it to the 355 nm dissociation of Cl[SUB2] and NO[SUB2] as well-understood test cases. In the Cl[SUB2] studies the velocity resolution obtained for the [SUP35]Cl fragments is on the order of δv/v=2.8% and for the first time we are able to directly observe dissociation via the weak B[SUP3]II[SUP+,SUBou] state channel whilst imaging the ground state Cl([SUP2]P[SUB3/2])-atom distribution. For the case of NO[SUB2] dissociation the internal state distributions of the NO fragment are extracted more cleanly using slicing than is possible with the Abel inversion and our resolution is sufficient to resolve some of the NO rotational structure in the kinetic energy release for the first time. Overall, we find our data to compare very favorably with previously reported... [ABSTRACT FROM AUTHOR]

Time-resolved photoelectron imaging was used to investigate the relaxation dynamics of electronically excited aniline in the gas-phase following ultraviolet irradiation in the 273-266 nm region. We find that at all wavelengths studied, excitation is predominantly to the long-lived (>1 ns) S1(ππ*) state, which exhibits ultrafast intramolecular vibrational redistribution on a <1 ps timescale. At excitation wavelengths centred on resonant transitions in the aniline absorption spectrum that have previously been assigned to the higher lying S2(3s/πσ*) state, we also see clear evidence of this state playing a role in the dynamics. However, we see no indication of any non-adiabatic coupling between the S1(ππ*) and S2(3s/πσ*) states over the range of excitation wavelengths studied. [ABSTRACT FROM AUTHOR]

We show that the photoionization dynamics of a small excited polyatomic molecule can be partially elucidated from the measurement of photoelectron angular distributions (PADs) at an energy resolution of only around 20 meV following excitation of various selected rotational levels in an excited electronic state. To illustrate this we present PADs corresponding to the formation of vibrationally resolved NH[sub 3][sup +] following the excitation of NH[sub 3] to selected rotational levels in its B˜ [sup 1]E[sup ″] electronic state. We also present a preliminary time-of-flight photoelectron spectrum showing peaks corresponding to resolved rotational levels of the NH[sub 3][sup +] ion. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present a crossed molecular beam scattering study, using velocity-map ion-imaging detection, of state-to-state rotational energy transfer for NO(A²Σ+) in collisions with the kinematically identical colliders He and D2. We report differential cross sections and angle-resolved rotational angular momentum polarization moments for transfer of NO(A, v = 0, N = 0, j = 0.5) to NO(A, v = 0, N' = 3, 5-12) in collisions with He and D2 at respective average collision energies of 670 cm-1 and 663 cm-1. Quantum scattering calculations on a literature ab initio potential energy surface for NO(A)-He [J. Kłos et al., J. Chem. Phys. 129, 244303 (2008)] yield near-quantitative agreement with the experimental differential scattering cross sections and good agreement with the rotational polarization moments. This confirms that the Kłos et al. potential is accurate within the experimental collisional energy range. Comparison of the experimental results for NO(A) + D2 and He collisions provides information on the hitherto unknown NO(A)-D2 potential energy surface. The similarities in the measured scattering dynamics of NO(A) imply that the general form of the NO(A)-D2 potential must be similar to that calculated for NO(A)-He. A consistent trend for the rotational rainbow maximum in the differential cross sections for NO(A) + D2 to peak at more forward angles than those for NO(A) + He is consistent with the NO(A)-D2 potential being more anisotropic with respect to NO(A) orientation. No evidence is found in the experimental measurements for coincident rotational excitation of the D2, consistent with the potential having low anisotropy with respect to D2. The NO(A) + He polarization moments deviate systematically from the predictions of a hard-shell, kinematic-apse scattering model, with larger deviations as N' increases, which we attribute to the shallow gradient of the anisotropic repulsive NO(A)-He potential energy surface. [ABSTRACT FROM AUTHOR]

We report time-resolved photoelectron imaging studies of gas-phase pyrrole over the 267-240 nm excitation region, recorded in conjunction with a 300 nm probe. Of specific interest is the lowest-lying (3s/πσ * ) state, which exhibits very weak oscillator strength but is thought to be excited directly at wavelengths ≤254 nm. We conclude, however, that the only significant contribution to our photoelectron data at all wavelengths investigated is from non-resonant ionization. Our findings do not rule out (3s/πσ * ) state excitation (as appears to be confirmed by supporting time-resolved ion-yield measurements) but do potentially highlight important caveats regarding the use and interpretation of photoreactant ionization measurements to interrogate dynamical processes in systems exhibiting significant topological differences between the potential energy surfaces of the neutral and cation states.

We present a crossed molecular beam scattering study, using velocity-map ion-imaging detection, of state-to-state rotational energy transfer for NO(A(2)Σ(+)) in collisions with the kinematically identical colliders He and D2. We report differential cross sections and angle-resolved rotational angular momentum polarization moments for transfer of NO(A, v = 0, N = 0, j = 0.5) to NO(A, v = 0, N' = 3, 5-12) in collisions with He and D2 at respective average collision energies of 670 cm(-1) and 663 cm(-1). Quantum scattering calculations on a literature ab initio potential energy surface for NO(A)-He [J. Kłos et al., J. Chem. Phys. 129, 244303 (2008)] yield near-quantitative agreement with the experimental differential scattering cross sections and good agreement with the rotational polarization moments. This confirms that the Kłos et al. potential is accurate within the experimental collisional energy range. Comparison of the experimental results for NO(A) + D2 and He collisions provides information on the hitherto unknown NO(A)-D2 potential energy surface. The similarities in the measured scattering dynamics of NO(A) imply that the general form of the NO(A)-D2 potential must be similar to that calculated for NO(A)-He. A consistent trend for the rotational rainbow maximum in the differential cross sections for NO(A) + D2 to peak at more forward angles than those for NO(A) + He is consistent with the NO(A)-D2 potential being more anisotropic with respect to NO(A) orientation. No evidence is found in the experimental measurements for coincident rotational excitation of the D2, consistent with the potential having low anisotropy with respect to D2. The NO(A) + He polarization moments deviate systematically from the predictions of a hard-shell, kinematic-apse scattering model, with larger deviations as N' increases, which we attribute to the shallow gradient of the anisotropic repulsive NO(A)-He potential energy surface.

We present the implementation of a new crossed-molecular beam, velocity-map ion-imaging apparatus, optimized for collisions of electronically excited molecules. We have applied this apparatus to rotational energy transfer in NO(A(2)Σ(+), v = 0, N = 0, j = 0.5) + Ar collisions, at an average energy of 525 cm(-1). We report differential cross sections for scattering into NO(A(2)Σ(+), v = 0, N' = 3, 5, 6, 7, 8, and 9), together with quantum scattering calculations of the differential cross sections and angle dependent rotational alignment. The differential cross sections show dramatic forward scattered peaks, together with oscillatory behavior at larger scattering angles, while the rotational alignment moments are also found to oscillate as a function of scattering angle. In general, the quantum scattering calculations are found to agree well with experiment, reproducing the forward scattering and oscillatory behavior at larger scattering angles. Analysis of the quantum scattering calculations as a function of total rotational angular momentum indicates that the forward scattering peak originates from the attractive minimum in the potential energy surface at the N-end of the NO. Deviations in the quantum scattering predictions from the experimental results, for scattering at angles greater than 10°, are observed to be more significant for scattering to odd final N'. We suggest that this represents inaccuracies in the potential energy surface, and in particular in its representation of the difference between the N- and O-ends of the molecule, as given by the odd-order Legendre moments of the surface.

The authors report time resolved photoelectron spectra of the (1)B(2)((1)Sigma(u) (+)) state of CS(2) at pump wavelengths in the region of 200 nm. In contrast to previous studies, the authors find that the predissociation dynamics is not well described by a single exponential decay. Biexponential modeling of the authors' data reveals a rapid decay pathway (tau<50 fs), in addition to a longer lived channel (tau approximately 350-650 fs) that displays a marked change in apparent lifetime when the polarization of the pump laser is rotated with respect to that of the probe. Since the initially populated (1)B(2)((1)Sigma(u) (+)) state may decay to form either S((1)D) or S((3)P) products (the latter produced via a spin-orbit induced crossing from a singlet to a triplet electronic surface), this lifetime observation may be rationalized in terms of changes in the relative ionization cross section of these singlet and triplet states of CS(2) as a function of laser polarization geometry. The experimentally observed lifetime of the longer lived channel is therefore a superposition of these two pathways, both of which decay on very similar time scales.