Photolysis Dynamics Laser Chemistry Lab

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. This journal is © the Owner Societies 2014.

A new reaction scheme is proposed to account for roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions, where nonadiabatic dynamics plays a key role and the collapse of superposition of wave functions is considered to be important in the beginning of the present scheme. Since the feature of molecular orbitals of reagents is crucial in reaction, we showed how to map out the spatial distribution of the relevant HOMO molecular orbitals of CH3Cl in the impact of fast electrons. We identified by experiment that the multiple overlap of nearby molecular orbitals affects even the vibrational motion of adjacent molecule DCl of the transient [ClDCl] chemical species. We also showed dynamical steric effects in the HBr + OH four-atom reaction as a manifestation of the nonadiabatic dynamics in complex systems. The roaming mechanism in the photo-initiated reaction of methyl formate is clarified in detail by experiment as well as the QCT trajectory calculation, where the conical intersection region plays an essential role. We suggest that two types of roaming trajectories coexist, i.e., deterministic and chaotic roaming trajectories based on classical trajectory calculations. To clarify the nonadiabatic dynamics in the roaming mechanism for non-collinear three-dimensional (3D) collisions, a new model of the 3D Polanyi rule is proposed as the extension of the well-established 2D Polanyi rule. In the 3D Polanyi rule, it is expected that the curvature and torsion of Frenet–Serret formulas in three-dimensional space would provide us key concepts in understanding reaction dynamics. © 2018, Accademia Nazionale dei Lincei.

Photodissociation of isobutyraldehyde (C3H7CHO) at 248 nm is investigated using time-resolved Fourier-transform infrared emission spectroscopy to demonstrate the growing importance of the roaming pathway with increasing molecular size of aliphatic aldehydes. Each acquired CO rotational distribution from v = 1 to 4 is well characterized by a single Boltzmann rotational temperature from 637 to 750 K, corresponding to an average rotational energy of 5.9 ± 0.6 kJ mol-1. The roaming signature that shows a small fraction of CO rotational energy disposal accompanied by a vibrationally hot C3H8 co-fragment is supported by theoretical prediction. The energy difference between the tight transition state (TS) and the roaming saddle point (SP) is found to be -27, 4, 15, 22, and 30 kJ mol-1 for formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, and 2,2-dimethyl propanal, respectively. The roaming SP is stabilized by a larger alkyl moiety. It is suggested that the roaming photodissociation rate of aldehydes increasingly exceeds those via the tight TS, resulting in the dominance of the CO + alkane products, as the size of aldehydes becomes larger. Along with formaldehyde, acetaldehyde, and propionaldehyde, in this work isobutyraldehyde is further demonstrated that this aldehyde family with special functional group is the first case in the organic compound to follow predominantly a roaming dissociation pathway, as the molecular size becomes larger. © the Owner Societies 2015.

In photodissociation of trans-formic acid (HCOOH) at 193 nm, we have observed two molecular channels of CO + H2O and CO2 + H2 by using 1 μs-resolved Fourier-transform infrared emission spectroscopy. With the aid of spectral simulation, the CO spectra are rotationally resolved for each vibrational state (v = 1–8). Each of the resulting vibrational and rotational population distributions is characteristic of two Boltzmann profiles with different temperatures, originating from either transition state pathway or OH-roaming to form the same CO + H2O products. The H2O roaming co-product is also spectrally simulated to understand the interplay with the CO product in the internal energy partitioning. Accordingly, this work has evaluated the internal energy disposal for the CO and H2O roaming products; especially the vibrational-state dependence of the roaming signature is reported for the first time. Further, given a 1 μs resolution, the temporal dependence of the CO/CO2 product ratio at v ≥ 1 rises from 3 to 10 of study, thereby characterizing the effect of conformational memory and well reconciling with the disputed results reported previously between absorption and emission methods. © 2020, The Author(s).

An alternative to the transition state (TS) pathway, the roaming route, which bypasses the minimum energy path but produces the same molecular products, was recently found in photodissociation dynamics. This account describes signatures of roaming in photodissociation of the carbonyl compounds, specifically methyl formate and aliphatic aldehydes. Methyl formate was promoted to the excited state, followed by internal conversion via a conical intersection. Then, the energetic precursor dissociated to fragments which proceeded along either TS or roaming path. In contrast to the lack of a roaming saddle point found in methyl formate, the structure of the roaming saddle point for each of a series of aliphatic aldehydes comprises two moieties that are weakly bound at a distance. As its size increases, the energy difference between the TS barrier and the roaming saddle point increases and the roaming pathway becomes increasingly dominant. Experimentally, the rotational-level dependence of the roaming route was measured with ion imaging, while the vibrational-state dependence was observed with time-resolved Fourier-transform infrared emission spectroscopy. The roaming signature was verified theoretically by quasi-classical trajectory (QCT) calculations. As an alternative to the QCT method, a multi-center impulsive model was developed to simulate the roaming scalar and vector properties. © 2018 Informa UK Limited, trading as Taylor & Francis Group.

This paper proposes a new type of roaming mechanism. We find a signature of trajectory with chaotic behavior in the action-angle diagram of the H + H2 reaction on a LEP surface, namely the trajectory is found to be very sensitive to the initial angle variable which corresponds to the phase of the H2 vibration. The trajectory pattern switches from the direct to the complex forming mechanism, and vice versa, in the angle range (0 ∼ π). In the complex forming angle range, trajectories switch from reactive to non-reactive randomly and suddenly, as the result, we cannot predict the collision pattern from the initial conditions. Therefore, we may classify such trajectory as a new type of roaming with chaotic behavior, and it is different from the ordinary trajectory with deterministic behavior. This chaotic behavior could be due cooperative nearby network interaction (CNN effect). We also suggest that the KPP (Kolmogorow-Petrovsky-Piskounov) equation is useful to estimate the density gradient of the activated reagents, so that one can evaluate the branching ratio to various exit channels, such as triple fragmentation, tight transition state, or the roaming channel with the aid of the present classical trajectory calculation. © 2017 Author(s).

The behavior of λ-doublet resolved rotational energy transfer (RET) by Ar collisions within the SH(X 2Π, v′=0) state is characterized. The matrix elements of terms in the interaction potential responsible for interference effects are calculated to explain the propensity rules for collision-induced transitions within and between spin-orbit manifolds. In this manner, the physical mechanisms responsible for the F 1-F 1, F 2-F 2, and F 1-F 2 transitions may be reasonably identified. As collision energy increases, the propensity for collisional population of the final e or f level is replaced by the e/f-conserving propensity. Such a change in propensity rule can be predicted in terms of energy sudden approximation at high J limit for the pure Hund's case scheme. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic hexapoles are revealed as a powerful tool in the rotational state-selection and alignment of molecules to be utilized in beam experiments on collisional and photoinitiated processes. In the paper, we report results on the application of the hexapolar technique on the recently studied chiral molecules propylene oxide, 2-butanol and 2-bromobutane, to be investigated in selective photodissociation and enantiomeric discrimination. © 2016 Author(s).

Multiple sensor systems are designed by varying aza-crown ether moiety in silicon quantum dots (SiQDs) for detecting individual Mg2+, Ca2+, and Mn2+ metal ions with significant selectivity and sensitivity. The detection limit of Mg2+, Ca2+, and Mn2+ can reach 1.81, 3.15, and 0.47 μM, respectively. Upon excitation of the SiQDs which are coordinated with aza-crown ethers, the photoinduced electron transfer (PET) takes place from aza-crown ether moiety to the valence band of SiQDs core such that the reduced probability of electron-hole recombination may diminish the subsequent fluorescence. The fluorescence suppression caused by such PET effect will be relieved after selective metal ion is added. The charge-electron binding force between the metal ion and aza-crown ether hinders the PET and thereby restores the fluorescence of SiQDs. The design of sensor system is based on the fluorescence "turn-on" of SiQDs while in search of the appropriate metal ion. For practical application, the sensing capabilities of metal ions in the live cells are performed and the confocal image results reveal their promising applicability as an effective and nontoxic metal ion sensor. © 2016 American Chemical Society.

Amine-functionalized graphitic carbon nitride (NH2/GCN) nanosheets photoluminescence, catalytic properties and excellent water dispersion stability were prepared and characterized by a variety of different analytical and spectroscopic techniques. The well-dispersed NH2/GCN nanosheets were found to exhibit remarkable pH sensing sensitivity at an ambient temperature with desirable broad detection range (1 ≤ pH ≤ 12). Moreover, upon incorporating silver nanoparticles (Ag NPs), the Ag-NH2/GCN nanocomposites showed excellent performances for catalytic reduction of 4-nitrophenol (4-NP) in NaBH4 with a superior rate constant (k) of 0.1594 s-1 within as short as 30 s. The NH2/GCN and Ag-NH2/GCN nanocomposites reported herein therefore render prospective applications as sensitive pH and practical catalytic applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The present study involves the synthesis, characterization, and catalytic application of ruthenium nanoparticles (Ru NPs) supported on plastic-derived carbons (PDCs) synthesized from plastic wastes (soft drink bottles) as an alternative carbon source. PDCs have been further activated with CO2 and characterized by various analytical techniques. The catalytic activity of Ru@PDC for the reduction of potassium hexacyanoferrate(III), (K3[Fe(CN)6]), and new fuchsin (NF) dye by NaBH4 was performed under mild conditions. The PDCs had spherical morphology with an average size of 0.5 μm, and the Ru NP (5 ± 0.2 nm) loading (4.01 wt %) into the PDC provided high catalytic performance for catalytic reduction of ferrocyanate(III) and NF dye. This catalyst can be recycled more than six times with only a minor loss of its catalytic activity. In addition, the stability and reusability of the Ru@PDC catalyst are also discussed. Copyright © 2018 American Chemical Society.

The simple and novel surfactant-free synthesis of flower-like strontium-doped nickel oxide nanorods (SNO NRs) via a simple sonochemical co-precipitation method was used for electrochemical sensing of quercetin (QCT). The structure and morphology of the as-synthesized flower-like SNO NRs were characterized using various spectroscopic techniques. Then, CV, EIS, and DPV were used to examine their electrochemical properties. The effective loading concentration, pH, scan rate and stability of the SNO NR-modified electrodes were studied. Under optimized conditions, the electrochemical detection of QCT demonstrated a low detection potential of 0.3 V (vs. Ag/AgCl), and achieved a higher oxidation peak current compared to those of other modified electrodes in PB (pH 5.0). The voltammetric current response was found to linearly increase with an increasing concentration range from 0.01-68.53 μM, along with a low detection limit of 1.98 nM, and a high sensitivity of 2.1055 μA mM cm-2. The sensor also shows good selectivity and satisfactory recovery for real sample (apple and grape juice) analysis. © 2020 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

The asymmetric-top molecule 2-bromobutane is oriented by means of a hexapole state selector; the angular distribution of the bromine atom photofragment, for the two fine-structure components, is acquired by velocity-map ion imaging. The molecular beam, spatially oriented along the time-of-flight axis, is intersected with a linearly polarized laser, whose polarization is tilted by 45° with respect to the detector surface. To obtain the mixing ratio of the perpendicular and parallel transitions, the fragment ion images and angular distributions can be appropriately simulated to give insight on the population mechanism of the specific electronic state involved at each selected excitation wavelength. The photofragment images obtained at 238.6 nm yielded an asymmetry factor β1 of 0.67, indicative of the extent of molecular orientation, and an anisotropy parameter β2 of 1.03, which is a signature of a prevailing parallel transition along the C-Br axis. When the photolysis wavelength is tuned to 254.1 nm, the corresponding angular distribution is less asymmetric (β1 = 0.24) and the obtained small value β2 = 0.12 is a characteristic of a predominantly perpendicular transition. The photofragment angular distributions are also affected by hexapole voltage, especially regarding the asymmetry factor, and this aspect provides information on the effect of molecular orientation. © 2017 Author(s).

Hexapole oriented 2-bromobutane is photodissociated and detected by a slice-ion-imaging technique at 234 nm. The laser wavelength corresponds to the C - Br bond breaking with emission of a Br atom fragment in two accessible fine-structure states: the ground state Br (2P3/2) and the excited state Br (2P1/2), both observable separately by resonance-enhanced multiphoton ionization (REMPI). Orientation is evaluated by time-of-flight measurements combined with slice-ion-imaging. © 2016 Author(s).

Both single-laser and two-laser experiments were conducted to look into the ion-imaging of Br*(2P1/2) and Br(2P3/2) photofragmented from 1-bromo-2-methylbutane in the range 232-240 nm via a detection scheme of (2+1) resonance-enhanced multiphoton ionization. The angular analysis of these photofragment distributions yields the anisotropy parameter β = 1.88 ± 0.06 for the Br∗ excited state which arises from a parallel transition, while β = 0.63 ± 0.09 for the Br ground state indicates the contribution from both a perpendicular transition and a non-adiabatic transition. When a hexapole coupled with an orienting field was implemented, the parent molecules are spatially oriented to yield an orientation efficiency |«cos θ »| of 0.15. Besides the χ angle between the recoil velocity v and the transition dipole moment μ, orienting molecules allows for the evaluation of the angle α between v and the permanent molecular dipole moment d. The angular analysis of Br∗ photofragment distribution yields χ = 11.5° and α in the range from 160° to 180° with weak dependency. In the two-laser experiments, the angular anisotropy of Br photofragment distribution was found to be smaller (0.38 ± 0.10) when the photolysis wavelength was red-shifted to 240 nm, suggesting the increasing contributions from perpendicular transitions. © 2019 American Chemical Society.

This paper aims at discussing new facets on stereodynamical behaviors in chemical reactions, i.e. the effects of molecular orientation and alignment on reactive processes. Further topics on macroscopic processes involving deviations from Arrhenius behavior in the temperature dependence of chemical reactions and chirality effects in collisions are also discussed. © 2015 AIP Publishing LLC.

The two-step microwave method was used to synthesize zinc oxide nanostars linked to graphene oxide (GO) nanosheets. The material was used to modify a screen printed carbon electrode (SPCE) and then explored as a binder-free electrocatalyst for the electrochemical determination of methyl parathion (MP). The morphology and crystallinity of the material were characterized by various techniques. The modified SPCE shows extraordinary electrochemical performances for sensitive determination of MP. Figures of merit include (a) a wide linear dynamic range (0.03–670 μM), (b) a low detection limit (1.2 nM; at S/N = 3), (c) a comparably low working voltage (−0.69 V vs. Ag/AgCl); and (d) an excellent sensitivity (16.5 μA μM−1 cm−2) that surpasses other modified electrodes. The sensor was successfully applied to the determination of MP, even in the presence of other common electroactive interference, in (spiked) fruits and vegetables. [Figure not available: see fulltext.]. © 2019, Springer-Verlag GmbH Austria, part of Springer Nature.

The first electronic excitation and adiabatic ionization energies of 35Cl and 37Cl 4-chlorostyrene were similar, with values of 33,977 ± 2 and 67,972 ± 5 cm−1, respectively. The general features in the obtained vibronic and cation spectra of the two isotopologues were similar. A frequency shift of 1–5 cm−1 was observed on many active vibrations of the 35Cl and 37Cl isotopologues of 4-chlorostyrene in the S1 and D0 states. This frequency difference at each mode may reflect the degree of Cl atom involvement in the overall vibration. © 2017 Elsevier B.V.

Herein, we report ultra-sensitive sensing of a prostate-specific antigen (PSA), which is used as a biomarker to detect prostate cancer, using a molybdenum series (MoO3, MoS2, and MoSe2) of two-dimensional nanosheets (2D NSs). Moreover, the design of a 2D NS-based PSA aptamer sensor system was demonstrated based on a fluorescence turn-on mechanism in the presence of a target. The 2D NSs acted as an excellent sensing platform in which the PSA aptamer was adsorbed on the NSs and subsequent energy transfer between them led to fluorescence quenching of the aptamer. The detection limit of PSA was achieved to be 13 pM for MoO3 NSs, whereas the MoS2 and MoSe2 systems exhibited a detection limit of 72 and 157 pM, respectively. To the best of our knowledge, this is the first report on the ultra-sensitive detection of a 2D NS-based aptamer sensor. The in vitro bioimaging measurements were performed using confocal fluorescence microscopy. Herein, PSA detection was successfully demonstrated in human embryonic kidney 293T (HEK) live cells. Moreover, the MoO3, MoS2, and MoSe2 NSs exhibit excellent biocompatibility and low toxicity; thus, these 2D NSs can be used as a promising sensor platform to detect prostate cancer. This journal is © The Royal Society of Chemistry.

This present study describes the synthesis of ultrafine Bi-Sn nanoparticles decorated on carbon aerogels (Bi-Sn NP/CAG) as a nanocomposite for the electrochemical simultaneous determination of dopamine (DA) and clozapine (CLZ). The typical characterization techniques, such as XRD, Raman, BET, FT-IR, TGA, XPS, and FE-SEM/TEM, showed useful insights into the crystal phase and morphology of Bi-Sn NP/CAG. Integrated Bi-Sn NP/CAG built into a cost-effective screen printed carbon electrode (SPCE) offers a high electrochemical surface area (ECSA) compared to unmodified, Bi-Sn, and CAG/SPCEs, such that it favourably allowed the binding of DA and CLZ molecules onto the surface at the Bi-Sn/CAG, which was demonstrated by cyclic and differential pulse voltammetry techniques. As a result, the DA and CLZ sensing exhibited low detection limits (DL, 4.6 and 97.6 nM (S/N = 3)), and sensitivity (3.402 and 0.4 μA μM-1 cm-2) over a wide linear range (0.02-97.59 and 0.5-2092 μM), respectively. To go a step further, the Bi-Sn NP/CAG/SPCE was applied for the simultaneous determination of DA and CLZ which featured lower DL (23.1 and 31.3 nM (S/N = 3)), and sensitivity (0.4979 and 0.04 μA μM-1 cm-2) over a wide linear range (2-182 and 10-910 μM), respectively. The selectivity for DA and CLZ in the presence of a 10-fold concentration of their potentially interfering active species was demonstrated. Finally, this sensing methodology enables the rapid electrochemical determination of the amount of DA and CLZ in a rat brain region serum sample with successful recovery outcomes. © The Royal Society of Chemistry.

In this work, gold nanoparticle (Au NP) decorated poly(diallyldimethylammonium chloride) (PDDA) functionalized graphene hydrogel (Au NP@PDDA/GH) nanocomposites were fabricated. The resulting materials were characterized by a variety of analytical and spectroscopic techniques. Electrochemical performances of the prepared composites were examined by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and linear sweep voltammetry (LSV). The Au NPs were decorated uniformly and densely on the GO@PDDA composite material based on the electrostatic attraction and this new hierarchical nanostructure can provide a more favourable microenvironment for electron transfer. Under the optimized conditions, the Au NP@PDDA/GH nanocomposite was used as a novel sensing probe for metronidazole (MZ) which was found to have the concentration range of 0.4-656.4 μM with a correlation coefficient (0.999, limit of detection (LOD) based on (LOD = 3k/∂) of 0.097 μM), and a sensitivity of 4.286 μA μM−1. With satisfactory selectivity, reproducibility, and stability, the nanostructure we proposed offered an alternative for electrode fabrication and MZ sensing. Au NP@PDDA/GH was also applied to the reduction of MZ and pharmacy tablets by NaBH4under ambient conditions. Thus, Au NP@PDDA/GH application provides simplicity, reliability, durability, and low cost benefits. © The Royal Society of Chemistry 2020.

In this work, we describe a facile fabrication of silver nanoparticles decorated on porous ultrathin two dimensional (2D) graphitic carbon nitride nanosheets (AgNPs@g-CN) via chemical approach, which was characterized by various analytical techniques including cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. As expected, the AgNPs@g-CN modified glassy carbon electrode (AgNPs@g-CN/GCE) exhibited remarkable electrocatalytic activity towards the detection of quercetin (QCR) with a wide linear range from 1.0 × 10−8 to 1.2 × 10−4 mol L−1 and a lower detection limit of 6.0 × 10−9 mol L−1. Besides, the amperometric results revealed that the peak current for QCR could not affect upon the sequential additions of electroactive interfering species such as metal ions (300 μM), biomolecules (100 μM), and other flavonoids (50 μM) indicating the selectivity of the proposed sensor. Moreover, the AgNPs@g-CN modified electrode displayed higher stability and reproducibility towards the detection of QCR. The AgNPs@g-CN/GCE could also be used to detect QCR in green apple (GA) samples with satisfactory recoveries for practical applications. The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and photocatalysis applications. © 2018 Elsevier B.V.

Steady-state and time-resolved fluorescence spectroscopy techniques were used to probe multifluorescence resulting from citric-acid-derived carbon dots (C-dots). Commonly, both carboxyl-/amine-functionalized C-dots exhibit three distinct emissive states corresponding to the carbon-core and surface domain. The shorter-wavelength fluorescence (below 400 nm) originates from the carbon-core absorption band at ∼290 nm, whereas the fluorescence (above 400 nm) is caused by two surface states at ∼350 and 385 nm. In addition to three emissive states, a molecular state was also found in amine-functionalized C-dots. Time-resolved emission spectra (TRES) and time-resolved area normalized emission spectra (TRANES) were analyzed to confirm the origin of excitation wavelength-dependent fluorescence of C-dots. The surface functional groups on the C-dots are capable of regulating the electron transfer to affect the multifluorescence behavior. The electron transfer takes place from the carbon-core to surface domain by the presence of -COOH on the surface and vice versa for the case of -NH2 present on the surface. To the best of our knowledge, this is the first report that the multiemissive states are probed in C-dots systems using TRES and TRANES analyses, and related fluorescence mechanisms are verified clearly. © 2015 American Chemical Society.

A molecular beam of halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) is focused by a hexapolar electrostatic field and photolyzed by UV laser radiation at 234 nm. Angular and speed distributions of chlorine and bromine photofragments emitted from halothane are measured for both spin-orbit states independently. Although the dissociation energy of the C-Cl bond is larger than that of C-Br, the relative yield of Cl to Br was found to be approximately 2. Measured speed and angular distributions of atomic fragments show distinct kinetic energy release and scattering characteristics: for bromine, observed fast and aligned fragments exhibit a signature of a direct mode of dissociation for the C-Br bond, via the electronically excited potential energy surface denoted nσ*(C-Br), of repulsive nature; for chlorine, a variation in the features is observed for the dissociation pathway through nσ*(C-Cl), from a modality similar to the bromine case, leading to fragments with appreciable kinetic energy release and pronounced directionality, to a modality involving slow products, nearly isotopically distributed. The origin of this behavior can be attributed to nonadiabatic interaction operating between the nσ*(C-Br) and nσ*(C-Cl) surfaces. These results are not only relevant for a detailed understanding of adiabatic versus diabatic coupling mechanisms in the manifold of excited states populated by photon absorption, but they also point out the possibility of selectively inducing specific dissociation pathways, even when involving energetically unfavorable outcomes, such as, in this case, the prevailing rupture of the stronger C-Cl bond against that of the weaker C-Br bond. Copyright © 2020 American Chemical Society.

Molecular orientation techniques are becoming available in the study of elementary chemical processes, in order to highlight those structural and dynamical properties that would be concealed by random rotational motions. Recently successful orientation was achieved for asymmetric-top and chiral molecules of much larger complexity than hitherto. In this work, we report and discuss the correlation between the vectors' photofragment recoil velocity v, transition dipole moment μ, and permanent dipole moment d in a dissociation experiment on hexapole oriented 2-bromobutane, photoinitiated by a linearly polarized laser. The sliced ion images of the Br∗(2P1/2) and Br(2P3/2) photofragments were acquired at 234.0 and 254.1 nm, respectively, by a (2 + 1) resonance-enhanced multiphoton ionization technique. A detailed analysis of the sliced ion images obtained at a tilting angle 45° of laser polarization provides information on the correlation of the three vectors, which are confined by two polar angles α and χ and one azimuthal angle φμd in the recoil frame. The sliced ion images of Br fragments eliminated individually from the enantiomers at 254.1 nm yield an asymmetric factor close to zero; for this reason the photofragment angular distributions do not show significant differences. The elimination of the Br∗ fragment at 234.0 nm is mainly correlated with a parallel transition, giving rise to a large anisotropy parameter of 1.85, and thus can be considered as a single state excitation. The resulting recoil frame angles are optimized to 163° ± 8° and 164° ± 1° for α and χ, respectively, whereas φμd is approaching 0° for the best fit. Since for the present molecule, the three vectors have an only slight spatial arrangement, the photofragment angular distributions of the two enantiomers do not show appreciable differences. Theoretical and computational simulations provide us the basis to state that oriented enantiomers can be discriminated on-the-fly in photodissociation processes even initiated by non-circularly polarized light, provided that the three vectors encountered above have specific three-dimensional arrangements. The fact that Br fragment elimination involves a multi-potential dissociation carries uncertainties in theoretical estimates of the vector direction. Therefore, this work represents a preliminary but significant step on the road to chiral discrimination on-the-fly, which is shown to be best propitiated in molecules where vectors are far from having degenerate mutual angular directions. © 2019 the Owner Societies.