Time-resolved Photoelectron Imaging Research Articles

Insights into ultrafast decay dynamics of electronically excited pyridine-N-oxide.

The ultrafast decay dynamics of pyridine-N-oxide upon excitation in the near-ultraviolet range of 340.2-217.6 nm is investigated using the femtosecond time-resolved photoelectron imaging technique. The time-resolved photoelectron spectra and photoelectron angular distributions at all pump wavelengths are carefully analyzed and the following view is derived: at the longest pump wavelengths (340.2 and 325.6 nm), pyridine-N-oxide is excited to the S1(1ππ*) state with different vibrational levels. The depopulation rate of the S1 state shows a marked dependence on vibrational energy and mode, and the lifetime is in the range of 1.4-160 ps. At 289.8 and 280.5 nm, both the second 1ππ* state and the S1 state are initially prepared. The former has an extremely short lifetime of ∼60 fs, which indicates that the ultrafast deactivation pathway such as a rapid internal conversion to one close-lying state is its dominant decay channel, while the latter is at high levels of vibrational excitation and decays within the range of 380-520 fs. At the shortest pump wavelengths (227.3 and 217.6 nm), another excited state of Rydberg character is mostly excited. We assign this state to the 3s Rydberg state which has a lifetime of 0.55-2.2 ps. This study provides a comprehensive picture of the ultrafast excited-state decay dynamics of the photoexcited pyridine-N-oxide molecule.

Channel Competition and Control of Relaxation Pathways in S1 State of Acrolein: Role of Conical Intersection and Surface Crossing.

Channel competition and further photochemical control of relaxation pathways in excited molecules are of primary importance in photochemistry and related areas. Acrolein, as the simplest and most typical α,β-enone, is suitable to provide a model for understanding the photochemistry and photophysics of α,β-enones. Here, the ultrafast dynamics in acrolein following S1(nπ*) excitation has been studied by time-resolved photoelectron imaging (TRPEI) and mass spectroscopy. The competition between intersystem crossing (ISC) and internal conversion (IC) is investigated. The key factor influencing the decay pathways and the relative contributions are revealed to be the position of the excitation relative to the energy of the S1/S0 conical intersection (CI), which is obtained to be 3.65-3.76 eV experimentally. If the excitation is above the CI, IC is superior to ISC and most excited molecules go back to the ground. Otherwise, ISC will dominate the relaxation and lead the triplet products formation. These results show the potential of affecting the dynamics and governing the fate of excited molecules by adjusting the excitation conditions from the point of view of chemical control.

The Value of Different Experimental Observables: A Transient Absorption Study of the Ultraviolet Excitation Dynamics Operating in Nitrobenzene.

Excess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340-750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al., J. Phys. Chem. A 2021, 125, 7174-7184]. Of note is the observation of a 1/e lifetime of 3.5-6.7 ps in the TAS data that was absent in the TRPEI measurements. This is interpreted as a dynamical signature of the T2 state in nitrobenzene─analogous to observations in the related nitronaphthalene system, and additionally supported by previous quantum chemistry calculations. The discrepancy between the TAS and TRPEI measurements is discussed, with the overall findings providing an example of how different spectroscopic techniques can exhibit varying sensitivity to specific steps along the overall reaction coordinate connecting reactants to photoproducts.

Rydberg state dynamics and fragmentation mechanism of N,N,N',N'-tetramethylmethylenediamine.

The non-adiabatic relaxation processes and the fragmentation dynamics of Rydberg-excited N,N,N',N'-tetramethylmethylenediamine (TMMDA) are investigated using femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. Excitation at 208nm populates TMMDA in a charge-localized 3p state. Rapid internal conversion (IC) to 3s produces two charge-delocalized conformers with independent time constants and distinct population ratios. As the system explores the 3s potential surface, the structural evolution continues on a 1.55ps timescale, followed by a slower (12.1ps) relaxation to the ground state. A thorough comparison of the time-dependent mass and photoelectron spectra suggests that ionization out of the 3p state ends up with the parent ion, the vibrational energy of which is insufficient for the bond cleavage. On the contrary, by virtue of the additional energy acquired by IC from 3p, the internal energy deposited in 3s is available to break the C-N bond, leading to the fragment ion. The fragmentation is found to occur on the ion surface instead of the Rydberg surface.

Mapping extended reaction coordinates in photochemical dynamics

Laser-based experiments facilitate numerous strategies for interrogating the complex non-adiabatic dynamics operating in the excited states of molecules. Measurements may be broadly separated into frequency- and time-resolved variants, with a combination of different approaches (with different associated observables) typically being required to reveal a complete mechanistic picture. In the former category, quantum state-resolved information may often be obtained using narrow linewidth lasers. This provides detailed information relating to the starting point on the photochemical reaction coordinate (via the absorption spectrum) and the asymptotic endpoints (i.e. the photoproducts). Direct observation of the intermediate pathways connecting these two limits is often not possible, however, due to the inherently long temporal duration of the laser pulses relative to the typical timescales of non-adiabatic energy redistribution processes. It is therefore desirable to obtain complementary information that monitors real-time evolution along the reaction coordinate as excited state population traverses the potential energy landscape. This may be achieved in time-resolved pump–probe experiments conducted using ultrafast (i.e. sub-picosecond) laser pulses. The use of valence state photoionization for the probe step is a commonly employed methodology and has proved highly instructive in revealing subtle mechanistic details of key energy redistribution pathways operating in many different molecular systems. One frequent limitation here, however, is the restricted “view” along the reaction coordinate(s) connecting the initially prepared excited states to various photoproducts. Guided by examples drawn from recent work using time-resolved photoelectron imaging, this review will discuss such issues in detail and highlight some strategies that potentially help overcome them – with particular emphasis placed on the advantages of projecting as deeply as possible into the ionization continuum. The role of complementary measurements using other spectroscopic techniques and the importance of high-level supporting theory to guide data interpretation will also be reinforced.

Structural dynamics upon photoinduced charge transfer in N,N,N′,N′-tetramethylmethylenediamine

The ultrafast structural motion linked to the charge transfer process in Rydberg excited N,N,N′,N′-tetramethylmethylenediamine (TMMDA) has been monitored in real time using femtosecond time-resolved photoelectron imaging coupled with quantum chemical calculations. Optical excitation to the 3 s Rydberg state initially populates the charge on one of the two amine groups, resulting in a charge-localized structure in the Franck-Condon (FC) region. As the wavepacket evolves on the 3 s potential surface, the molecular geometry changes with time, leading to the corresponding variation in the charge distribution. The ensuing structural evolution yields two distinct conformers GG+ and TT+ (see text for nomenclature), both with the charge delocalized between the two nitrogen atoms. By virtue of the sensitivity of the Rydberg electron binding energy (BE) on the nuclear geometry, the time-dependent BE spectrum offers an intuitive mapping of the charge transfer reaction that leads from the initially prepared charge-localized GG-FC structure to the fully charge-delocalized GG+ and TT+ structures. Complementary computations provide evidence that through-space interaction is responsible for the charge delocalization in the GG+ and TT+ structures.

Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution.

Fluorescent labelling of macromolecular samples, including using the green fluorescent protein (GFP), has revolutionised the field of bioimaging. The ongoing development of fluorescent proteins require a detailed understanding of the photophysics of the biochromophore, and how chemical derivatisation influences the excited state dynamics. Here, we investigate the photophysical properties associated with the S1 state of three alkylated derivatives of the chromophore in GFP, in the gas phase using time-resolved photoelectron imaging, and in water using femtosecond fluorescence upconversion. The gas-phase lifetimes (1.6-10 ps), which are associated with the intrinsic (environment independent) dynamics, are substantially longer than the lifetimes in water (0.06-3 ps), attributed to stabilisation of both twisted intermediate structures and conical intersection seams in the condensed phase. In the gas phase, alkylation on the 3 and 5 positions of the phenyl ring slows the dynamics due to inertial effects, while a 'pre-twist' of the methine bridge through alkylation on the 2 and 6 positions significantly shortens the excited state lifetimes. Formation of a minor, long-lived (≫ 40 ps) excited state population in the gas phase is attributed to intersystem crossing to a triplet state, accessed because of a T1/S1 degeneracy in the so-called P-trap potential energy minimum associated with torsion of the single-bond in the bridging unit connecting to the phenoxide ring. A small amount of intersystem crossing is supported through TD-DFT molecular dynamics trajectories and MS-CASPT2 calculations. No such intersystem crossing occurs in water at T = 300 K or in ethanol at T ≈ 77 K, due to a significantly altered potential energy surface and P-trap geometry.

Excitation wavelength dependent S1-state decay dynamics of 2-aminopyridine and 3-aminopyridine.

The decay dynamics of 2-aminopyridine and 3-aminopyridine excited to the S1 state is investigated using femtosecond time-resolved photoelectron imaging. The lifetime of the S1 state for both molecules shows a rapid decrease with the increase of the vibrational energy. It is shown that, besides intersystem crossing to the lower-lying triplet state of T1, the decay to the ground state (S0) via internal conversion through a conical intersection plays an increasingly important role and becomes dominant for vibrational states well above the S1 state origin. The comparison between 2-aminopyridine and 3-aminopyridine suggests that the intramolecular hydrogen bonding between a hydrogen atom of the NH2 group and the heterocyclic nitrogen atom in 2-aminopyridine effectively hinders the ring deformation at lower vibrational states which is required for the wavepacket to reach the S1/S0 conical intersection, and therefore slows down the S1 to S0 internal conversion.

Wavepacket dynamics of the excited (S1) state of 2,5-difluoroaniline by accidental resonance with the Rydberg states.

Coherent nuclear wavepacket behavior obtained by time-resolved spectroscopy is a good choice to capture the real-time evolution of molecular configuration. Using femtosecond time-resolved photoelectron imaging, we investigate the real-time evolution of the vibrational wavepacket of 2,5-difluoroaniline following the coherent excitation of an out-of-plane vibrational mode in the S1 state at 289.8nm. Probed by an accidental resonance with the Rydberg states, the periodic oscillations with the frequency of 99cm-1 are observed from the photoelectron kinetic energy (PKE) distributions, corresponding to the energy difference between the out-of-plane mode X1 0 of C-F bond and the band origin. Moreover, phase reversal of π rad between 0.66-0.75 and 1.00-1.08eV is also observed in the PKE region. Combined with the scan of the potential energy surface in the ground cationic D0 state, the observed two ionization channels corresponding to different phases are attributed to the periodic geometry changes between the planar and the non-planar structures when the coherent wavepacket evolves from the initial vertical Franck-Condon region toward the global minimum of the S1 potential energy surface.

A Hückel Model for the Excited-State Dynamics of a Protein Chromophore Developed Using Photoelectron Imaging.

ConspectusChemistry can be described as the movement of nuclei within molecules and the concomitant instantaneous change in electronic structure. This idea underpins the central chemical concepts of potential energy surfaces and reaction coordinates. To experimentally capture such chemical change therefore requires methods that can probe both the nuclear and electronic structure simultaneously and on the time scale of atomic motion. In this Account, we show how time-resolved photoelectron imaging can do exactly this and how it can be used to build a detailed and intuitive understanding of the electronic structure and excited-state dynamics of chromophores. The chromophore of the photoactive yellow protein (PYP) is used as a case study. This chromophore contains a para-substituted phenolate anion, where the substituent, R, can be viewed as an acrolein derivative. It is shown that the measured photoelectron angular distribution can be directly related to the electronic structure of the para-substituted phenolate anion. By incrementally considering differing R groups, it is also shown that these photoelectron angular distributions are exquisitely sensitive to the conformational flexibility of R and that when R contains a π-system the excited states of the chromophore can be viewed as a linear combination of the π* molecular orbitals on the phenolate (πPh*) and the R substituent (πR*). Such Hückel treatment shows that the S1 state of the PYP chromophore has predominantly πR* character and that it is essentially the same as the chromophore of the green fluorescent protein (GFP). The S1 excited-state dynamics of the PYP chromophore probed by time-resolved photoelectron imaging clearly reveals both structural (nuclear) dynamics through the energy spectrum and electronic dynamics through the photoelectron angular distributions. Both motions can be accurately assigned using quantum chemical calculations, and these are consistent with the intuitive Hückel treatment presented. The photoactive protein chromophores considered here are examples of where a chemists’ intuitive Hückel view for ground-state chemistry appears to be transferable to the prediction of photochemical excited-state reactivity. While elegant and insightful, such models have limitations, including nonadiabatic dynamics, which is present in a related PYP chromophore, where a fraction of the S1 state population forms a nonvalence (dipole-bound) state of the anion.

The ultrafast nonradiative processes and photodissociation dynamics investigation of S1 state in propanal.

The ultrafast nonradiative dynamics in the S1 electronic excited state and the corresponding photodissociation dynamics in propanal molecules have been studied with time-resolved photoelectron imaging and time-of-flight mass spectrometry at an excitation wavelength of 320nm. The population of the S1 state undergoes ultrafast internal conversion (IC) to the highly vibrationally hot S0 state in a timescale of <100fs and nonradiative deactivation by intersystem crossing (ISC) to triplet T1 state occurring with a time constant of about several hundreds of femtoseconds. The ISC process is then followed by the dissociation on the T1 surface because the excitation energy is higher than the dissociation barrier along the C-C(HO) bond length coordinate. The dissociation product of the CHO radical has an appearance time of about 540fs, which agrees well with the measured ISC relaxation time constant of 430fs. The CO molecule is proposed to form at about 170fs after the excitation, supporting the dissociation mechanism via the molecular channel following the IC decay of the S1 state. The energy of the first excited electronic state of the C3H6O+ is obtained to be 12.25eV.

Photochemical carbon-sulfur bond cleavage in thioethers mediated via excited state Rydberg-to-valence evolution.

Time-resolved photoelectron imaging and supporting ab initio quantum chemistry calculations were used to investigate non-adiabatic excess energy redistribution dynamics operating in the saturated thioethers diethylsulfide, tetrahydrothiophene and thietane. In all cases, 200 nm excitation leads to molecular fragmentation on an ultrafast (<100 fs) timescale, driven by the evolution of Rydberg-to-valence orbital character along the S-C stretching coordinate. The C-S-C bending angle was also found to be a key coordinate driving initial internal conversion through the excited state Rydberg manifold, although only small angular displacements away from the ground state equilibrium geometry are required. Conformational constraints imposed by the cyclic ring structures of tetrahydrothiophene and thietane do not therefore influence dynamical timescales to any significant extent. Through use of a high-intensity 267 nm probe, we were also able to detect the presence of some transient (bi)radical species. These are extremely short lived, but they appear to confirm the presence of two competing excited state fragmentation channels - one proceeding directly from the initially prepared 4p manifold, and one involving non-adiabatic population of the 4s state. This is in addition to a decay pathway leading back to the S0 electronic ground state, which shows an enhanced propensity in the 5-membered ring system tetrahydrothiophene over the other two species investigated.

Photo-isomerization of the isolated photoactive yellow protein chromophore: what comes before the primary step?

Photoactive proteins typically rely on structural changes in a small chromophore to initiate a biological response. While these changes often involve isomerization as the "primary step", preceding this is an ultrafast relaxation of the molecular framework caused by the sudden change in electronic structure upon photoexcitation. Here, we capture this motion for an isolated model chromophore of the photoactive yellow protein using time-resolved photoelectron imaging. It occurs in <150 fs and is apparent from a spectral shift of ∼70 meV and a change in photoelectron anisotropy. Electronic structure calculations enable the quantitative assignment of the geometric and electronic structure changes to a planar intermediate from which the primary step can then proceed.

Spectroscopic application of few-femtosecond deep-ultraviolet laser pulses from resonant dispersive wave emission in a hollow capillary fibre.

We exploit the phenomenon of resonant dispersive wave (RDW) emission in gas-filled hollow capillary fibres (HCFs) to realize time-resolved photoelectron imaging (TRPEI) measurements with an extremely short temporal resolution. By integrating the output end of an HCF directly into a vacuum chamber assembly we demonstrate two-colour deep ultraviolet (DUV)-infrared instrument response functions of just 10 and 11 fs at central pump wavelengths of 250 and 280 nm, respectively. This result represents an advance in the current state of the art for ultrafast photoelectron spectroscopy. We also present an initial TRPEI measurement investigating the excited-state photochemical dynamics operating in the N-methylpyrrolidine molecule. Given the substantial interest in generating extremely short and highly tuneable DUV pulses for many advanced spectroscopic applications, we anticipate our first demonstration will stimulate wider uptake of the novel RDW-based approach for studying ultrafast photochemistry – particularly given the relatively compact and straightforward nature of the HCF setup.

Ultrafast decay dynamics of 2-hydroxypyridine excited to S1 electronic state

The S1 state decay dynamics of 2-hydroxypyridine following UV excitation at a wavelength range of 276.9−250.0 nm is investigated using femtosecond time-resolved photoelectron imaging technique. Based on pump wavelength dependence of the decay dynamics, a refined decay picture is proposed. At pump wavelength of 276.9 nm, the S1 state is depopulated through intersystem crossing to lower triplet state(s). At 264.0 nm, both intersystem crossing to lower triplet state(s) and internal conversion to the ground state are in operation. At 250.0 nm, internal conversion to the ground state becomes dominated.

Nonadiabatic Dynamics between Valence, Nonvalence, and Continuum Electronic States in a Heteropolycyclic Aromatic Hydrocarbon.

Internal conversion between valence-localized and dipole-bound states is thought to be a ubiquitous process in polar molecular anions, yet there is limited direct evidence. Here, photodetachment action spectroscopy and time-resolved photoelectron imaging with a heteropolycyclic aromatic hydrocarbon (hetero-PAH) anion, deprotonated 1-pyrenol, is used to demonstrate a subpicosecond (τ1 = 160 ± 20 fs) valence to dipole-bound state internal conversion following excitation of the origin transition of the first valence-localized excited state. The internal conversion dynamics are evident in the photoelectron spectra and in the photoelectron angular distributions (β2 values) as the electronic character of the excited state population changes from valence to nonvalence. The dipole-bound state subsequently decays through mode-specific vibrational autodetachment with a lifetime τ2 = 11 ± 2 ps. These internal conversion and autodetachment dynamics are likely common in molecular anions but difficult to fingerprint due to the transient existence of the dipole-bound state. Potential implications of the present excited state dynamics for interstellar hetero-PAH anion formation are discussed.

Ultraviolet Excitation Dynamics of Nitrobenzenes

Time-resolved photoelectron imaging was used to investigate nonadiabatic processes operating in the excited electronic states of nitrobenzene and three methyl-substituted derivatives: 3,5-, 2,6-, and 2,4-dimethylnitrobenzene. The primary goal was evaluating the dynamical impact of the torsional angle between the NO2 group and the benzene ring plane-something previously implicated in mediating the propensity for branching into different photodissociation pathways (NO vs NO2 elimination). Targeted, photoinitiated release of NO radicals is of interest for clinical medicine applications, and there is a need to establish basic structure-dynamics-function principles in systematically varied model systems following photoexcitation. Within our 200 ps experimental detection window, we observed no significant differences in the excited-state lifetimes exhibited by all species under study using a 267 nm pump and ionization with an intense 400 nm probe. In agreement with previous theoretical predictions, this suggests that the initial energy redistribution dynamics within the singlet and triplet manifolds are driven by motions localized predominantly on the NO2 group. Our findings also imply that both NO and NO2 elimination occur from a vibrationally hot ground state on extended (nanosecond) timescales, and any variations in NO vs NO2 branching upon site-selective methylation are due to steric effects influencing isomerization prior to dissociation.

Ultrafast Dynamics of the Isolated Adenosine-5'-triphosphate Dianion Probed by Time-Resolved Photoelectron Imaging.

The excited state dynamics of the doubly deprotonated dianion of adenosine-5'-triphosphate, [ATP-H2]2-, has been spectroscopically explored by time-resolved photoelectron spectroscopy following excitation at 4.66 eV. Time-resolved photoelectron spectra show that two competing processes occur for the initially populated 1ππ* state. The first is rapid electron emission by tunneling through a repulsive Coulomb barrier as the 1ππ* state is a resonance. The second is nuclear motion on the 1ππ* state surface leading to an intermediate that no longer tunnels and subsequently decays by internal conversion to the ground electronic state. The spectral signatures of the features are similar to those observed for other adenine-derivatives, suggesting that this nucleobase is quite insensitive to the nearby negative charges localized on the phosphates, except of course for the appearance of the additional electron tunneling channel, which is open in the dianion.

Time-resolved photoelectron imaging of complex resonances in molecular nitrogen.

We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702-19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.

Ultrafast dynamics of electron excited states of phenylacetylene

Interaction of light with matter has always been important in the field of natural science. Particularly, the ultrafast radiationless relaxation induced by UV light of molecular electronic excited states accompanied by ultrafast energy transfer plays an important role in the natural photophysical, photochemical and biological reactions. Generally, the molecular electronic excited state can be deactivated through a variety of decay channels, including dissociation, isomerization, internal conversion, intersysterm crossing, vibrational energy redistribution, and autoionization. This complexity of relaxation channels brings about a wide variety of deactivation mechanisms. The ultrafast nonadibatic relaxation dynamics of the excited state of phenylacetylene is studied by using femtosecond time-resolved photoelectron imaging and femtosecond time-resolved mass spectrometry. The first excited state S&lt;sub&gt;2&lt;/sub&gt; of phenylacetylene is excited by 235 nm pump light, and the excited state deactivation process is detected by 400 nm probe light. The time-dependent curves of parent ions include two exponential curves. One is the fast component with a time constant of 116 fs, and the other is the slow component with a time constant of 106 ps. The time-resolved photoelectron kinetic energy distribution is obtained from the time-resolved photoelectron images. Combined with the time-resolved photoelectron spectroscopy data, the fast component with a time constant of 116 fs is found to reflect the internal conversion process from S&lt;sub&gt;2&lt;/sub&gt; state to S&lt;sub&gt;1&lt;/sub&gt; state. The experimental results also show that S&lt;sub&gt;1&lt;/sub&gt; state is arranged by internal conversion, and the inter system jump process to T&lt;sub&gt;1&lt;/sub&gt; state is an important attenuation channel. This work provides a clearer physical picture for S&lt;sub&gt;1&lt;/sub&gt; state nonadibatic relaxation dynamics of phenylacetylene.