Time-resolved Coulomb Explosion Research Articles

X-ray induced Coulomb explosion imaging of transient excited-state structural rearrangements in CS2

Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation.

Time-Domain Rotational Raman Spectroscopy of the Ethylene Dimer and Trimer by Coulomb Explosion Imaging of Rotational Wave Packets.

We report rotational Raman spectroscopy of the ethylene dimer and trimer, based on time-resolved Coulomb explosion imaging of rotational wave packets. Rotational wave packets were created in the gas-phase ethylene clusters upon nonresonant ultrashort pulse irradiation. The subsequent rotational dynamics were traced as spatial distribution of monomer ions ejected from the clusters via the Coulomb explosion process induced by a strong probe pulse. The observed images of monomer ions show multiple kinetic energy components. The time-dependence of the angular distribution for each component was analyzed, and the Fourier transformation spectra, which correspond to rotational spectra, were obtained. A lower kinetic energy component was mainly attributed to a signal from the dimer and a higher energy component mainly from the trimer. We have successfully observed rotational wave packets up to a delay time of ∼20 ns and achieved a spectral resolution of 70 MHz after Fourier transformation. Owing to this higher resolution than the previous studies, improved rotational and centrifugal distortion constants were obtained from the spectra. In addition to improving the spectroscopic constants, this study opens the way for rotational spectroscopy of larger molecular clusters than dimers through Coulomb explosion imaging of rotational wave packets. Details of spectral acquisition and analyses of each kinetic energy component are also reported.

Rotational wave-packet imaging spectroscopy of the ethylene dimer

We report time-domain rotational spectroscopy of the ethylene dimer, (C2H4)2, by implementing time-resolved Coulomb explosion imaging. A molecular movie of rotational wave packets of the dimer has been captured with a delay time of up to 11 ns. Pure rotational spectrum of the cluster is obtained with frequency resolution of ∼ 120 MHz by Fourier transformation of the time trace of the alignment parameter. Rotational and centrifugal distortion constants are determined with much improved precision than the previous infrared studies. The present study demonstrates the capability of the newly developed time-domain approach in rotational spectroscopy of weakly bound nonpolar clusters.

Rotational spectroscopy of the argon dimer by time-resolved Coulomb explosion imaging of rotational wave packets

We report time-domain rotational spectroscopy of the argon dimer, Ar2, by implementing time-resolved Coulomb explosion imaging of rotational wave packets. The rotational wave packets are created in Ar2 with a linearly polarized, nonresonant, ultrashort laser pulse, and their spatiotemporal evolution is fully characterized by measuring angular distribution of the fragmented Ar+ promptly ejected from Ar22+ generated by the more intense probe pulse. The pump-probe measurements have been carried out up to a delay time of 16 ns. The alignment parameters, derived from the observed images, exhibit periodic oscillation lasting for more than 15 ns. The pure rotational spectrum of Ar2 is obtained by Fourier transformation of the time traces of the alignment parameters. The frequency resolution in the spectrum is about 90 MHz, the highest ever achieved for Ar2. The rotational constant and the centrifugal distortion constant are determined with much improved precision than the previous experimental results: B0 = 1.72713 ± 0.00009 GHz and D0 = 0.0310 ± 0.0005 MHz. The present B0 value does not match within the quoted experimental uncertainty with that from the VUV spectroscopy, so far accepted as an experimental reference to assess theories. The present improved constants would stand as new references to calibrate state-of-the-art theoretical investigations and an indispensable experimental source for the construction of an accurate empirical intermolecular potential.

Tracking the nuclear movement of the carbonyl sulfide cation after strong-field ionization by time-resolved Coulomb-explosion imaging

We studied the ultrafast nuclear dynamics during the dissociation of ${\mathrm{OCS}}^{+}$ molecules using a strong IR-laser pump and probe technique in combination with the coincidence measurement. The nuclear movement is tracked by analyzing the time-dependent kinetic energy release (KER) spectra. The involved dissociation states and pathways are assigned with the help of the semiclassical Landau-Zener surface hopping calculations. The real-time bond-breaking dynamics of the ${3}^{2}\phantom{\rule{0.16em}{0ex}}A{}^{\ensuremath{'}}$ coupling to other states are observed for the two-body dissociation channel and the three-body dissociation channel but with high KER. The three-body dissociation channel with low KER is assigned to the direct breaking process from the ${3}^{2}\phantom{\rule{0.16em}{0ex}}A{}^{\ensuremath{''}}$ state. The overall agreements between the experimental and theoretical results demonstrate that the time-resolved Coulomb-explosion imaging is a valuable way to monitor the bond breaking and structural evolution of complex molecules.

Capturing roaming molecular fragments in real time.

Since the discovery of roaming as an alternative molecular dissociation pathway in formaldehyde (H2CO), it has been indirectly observed in numerous molecules. The phenomenon describes a frustrated dissociation with fragments roaming at relatively large interatomic distances rather than following conventional transition-state dissociation; incipient radicals from the parent molecule self-react to form molecular products. Roaming has been identified spectroscopically through static product channel-resolved measurements, but not in real-time observations of the roaming fragment itself. Using time-resolved Coulomb explosion imaging (CEI), we directly imaged individual "roamers" on ultrafast time scales in the prototypical formaldehyde dissociation reaction. Using high-level first-principles simulations of all critical experimental steps, distinctive roaming signatures were identified. These were rendered observable by extracting rare stochastic events out of an overwhelming background using the highly sensitive CEI method.

Roaming dynamics in real time

Chemical Physics Roaming is distinct from conventional reaction channels because of the unusual geometries that chemical systems use to bypass the minimum energy pathway. It is a relatively new phenomenon that is usually determined in experiments through spectroscopic characterization of the roaming products. Using a combination of time-resolved Coulomb explosion imaging and quasiclassical trajectory analysis, Endo et al. report real-time observation of individual fragments of the prototypical reaction of deuterated formaldehyde (D2CO) dissociation as they roam on ultrafast time scales. They show that roaming not only occurs several orders of magnitude earlier than previously expected but also that it can terminate in a radical (D + DCO) rather than the well-known molecular (D2 + CO) product channel. Science , this issue p. [1072][1] [1]: /lookup/doi/10.1126/science.abc2960

Time-resolved site-selective imaging of predissociation and charge transfer dynamics: the CH3I B-band

The predissociation dynamics of the 6s (B2E) Rydberg state of gas-phase CH3I were investigated by time-resolved Coulomb-explosion imaging using extreme ultraviolet (XUV) free-electron laser pulses. Inner-shell ionization at the iodine 4d edge was utilized to provide a site-specific probe of the ensuing dynamics. The combination of a velocity-map imaging (VMI) spectrometer coupled with the pixel imaging mass spectrometry (PImMS) camera permitted three-dimensional ionic fragment momenta to be recorded simultaneously for a wide range of iodine charge states. In accord with previous studies, initial excitation at 201.2 nm results in internal conversion and subsequent dissociation on the lower-lying A-state surface on a picosecond time scale. Examination of the time-dependent yield of low kinetic energy iodine fragments yields mechanistic insights into the predissociation and subsequent charge transfer following multiple ionization of the iodine products. The effect of charge transfer was observed through differing delay-dependencies of the various iodine charge states, from which critical internuclear distances for charge transfer could be inferred and compared to a classical over-the-barrier model. Time-dependent photofragment angular anisotropy parameters were extracted from the central slice of the Newton sphere, without Abel inversion, and highlight the effect of rotation of the parent molecule before dissociation, as observed in previous works. Our results demonstrate the ability to perform three-dimensional ion imaging at high event rates and showcase the potential benefits of this approach, particularly in relation to further time-resolved studies at free-electron laser facilities.

Direct imaging of direction-controlled molecular rotational wave packets created by a polarization-skewed double-pulse.

High-precision, time-resolved Coulomb explosion imaging of rotational wave packets in nitrogen molecules created with a pair of time-delayed, polarization-skewed femtosecond laser pulses is presented, providing insight into the creation process and dynamics of direction-controlled wave packets. To initiate unidirectional rotation, the interval of the double-pulse was set so that the second, polarization-tilted pulse hit the molecules at the time when molecules were aligned or antialigned along the polarization vector of the first pulse. During the revival period of the rotational wave packet, pulse intervals around both the full and half revival times were used. The observed molecular wave packet movies clearly show the signatures of quantum rotation, such as angular localization (alignment), dispersion, and revival phenomena, during the unidirectional motion. The patterns are quite different depending on the pulse interval even when the angular distribution at the second pulse irradiation is similar. The observed interval-dependence of the dynamics was analyzed on the basis of the real-time images, with the aid of numerical simulations, and the creation process of the packets was discussed. We show that the observed image patterns can be essentially rationalized in terms of rotational period and alignment parameter. Because the double-pulse scheme is the most fundamental in the creation of direction-controlled rotational wave packets, this study will lead to more sophisticated control and characterization of directional molecular motions.

Making Sense of Coulomb Explosion Imaging.

A multifaceted agreement between ab initio theoretical predictions and experimental measurements, including branching ratios, channel-specific kinetic energy release, and three-body momentum correlation spectra, leads to the identification of new mechanisms in Coulomb-explosion (CE) induced two- and three-body breakup processes in methanol. These identified mechanisms include direct nonadiabatic Coulomb explosion responsible for CO bond-breaking, a long-range " inverse harpooning" dominating the production of H2+ + HCOH+, a transient proton migration leading to surprising energy partitioning in three-body fragmentation and other complex dynamics forming products such as H2O+ and H3+. These mechanisms provide general concepts that should be useful for analyzing future time-resolved Coulomb explosion imaging of methanol as well as other molecular systems. These advances are enabled by a combination of recently developed experimental and computational techniques, using weak ultrafast EUV pulses to initiate the CE and a high-level quantum chemistry approach to follow the resulting field-free nonadiabatic molecular dynamics.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Coulomb-explosion imaging of concurrent CH2BrI photodissociation dynamics

The dynamics following laser-induced molecular photodissociation of gas-phase CH$_{2}$BrI at 271.6 nm were investigated by time-resolved Coulomb explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH$_{2}$BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH$_{2}$Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb explosion imaging as a real-time probe of chemical dynamics.

Time-resolved Four-body Coulomb Explosion Imaging of Correlated Dynamics of Hydrogen Atoms in Acetylene Dication

The correlated motion of the two deuterium atoms associated with the hydrogen migration and structural deformation to non-planar geometry are identified in acetylene dication by the time-resolved four-body Coulomb explosion imaging.

First-principles molecular-dynamics simulation of biphenyl under strong laser pulses by time-dependent density-functional theory

The femtosecond laser reaction dynamics of the 3,5-difluoro-3\ensuremath{'},5\ensuremath{'}-dibromo-biphenyl (DFDBrBPh) molecule is investigated using time-dependent density-functional theory combined with molecular-dynamics (TDDFT-MD) simulation. This work is based on a recent experiment that monitored torsional motion of the DFDBrBPh molecule by femtosecond time-resolved Coulomb explosion imaging [Madsen et al., Phys. Rev. Lett. 102, 073007 (2009)]. The results confirm that the probe pulse triggers a Coulomb explosion and the kick pulse induces the torsional motion of two phenyl rings, using the experimental settings of the lasers. The Coulomb explosion dynamics simulation verifies that the F and Br atoms dissociate to the ion detector while maintaining their initial alignment with respect to the phenyl rings, which is the fundamental basis of Coulomb explosion imaging of molecular torsion. Furthermore, the period and amplitude of the torsional motion obtained by the simulation are consistent with the experimental values. This validates the ability of the TDDFT-MD method to reveal the underlying mechanism of experimentally observed molecular torsional dynamics.

Control and femtosecond time-resolved imaging of torsion in a chiral molecule

We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3',5'-dibromo-4'-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds (ps), torsion occurs with a period of 1.25 ps and an amplitude of 3° in excellent agreement with theoretical calculations. At larger times, the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured. We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data.

Time-resolved Coulomb-explosion imaging of nuclear wave-packet dynamics induced in diatomic molecules by intense few-cycle laser pulses

We studied the nuclear dynamics in diatomic molecules (N${}_{2}$, ${\mathrm{O}}_{2}$, and CO) following their interaction with intense near-IR few-cycle laser pulses. Using Coulomb-explosion imaging in combination with the pump-probe approach, we mapped dissociation pathways of those molecules and their molecular ions. We identified all symmetric and asymmetric breakup channels for molecular ions up to ${\mathrm{N}}_{2}^{5+}$, ${\mathrm{O}}_{2}^{4+}$, and CO${}^{4+}$. For each of those channels we measured the kinetic energy release (KER) spectra as a function of delay between the pump and probe pulses. For both ${\mathrm{N}}_{2}$ and ${\mathrm{O}}_{2}$ the asymmetric (3,1) channel is only observed for short (20 fs) delays and completely disappears after that. We interpret this observation as a signature of electron localization taking place in dissociating molecular tri-cations when their internuclear separation reaches about 2.5 times the equilibrium bond length. This is a direct confirmation that electron localization plays an essential role in the universal mechanism of enhanced ionization in homonuclear diatomic molecules. Using classical and quantum mechanical simulations of the time-dependent KER spectra, we identify the pathways and intermediate states involved in the laser-induced dissociation of those molecules.

Visualizing hydrogen atoms migrating in acetylene dication by time-resolved three-body and four-body Coulomb explosion imaging

The visualization of ultrafast isomerization of deuterated acetylene dication (C(2)D(2)(2+)) is demonstrated by time-resolved Coulomb explosion imaging with sub-10 fs intense laser pulses (9 fs, 0.13 PW cm(-2), 800 nm). The Coulomb explosion imaging monitoring the three-body explosion process, C(2)D(2)(3+)→ D(+) + C(+) + CD(+), as a function of the delay between the pump and probe pulses revealed that the migration of a deuterium atom proceeds in a recurrent manner; One of the deuterium atoms first shifts from one carbon site to the other in a short timescale (∼90 fs), and then migrates back to the original carbon site by 280 fs, in competition with the molecular dissociation. Correlated motion of the two deuterium atoms associated with the hydrogen migration and structural deformation to non-planar geometry are identified by the time-resolved four-body Coulomb explosion imaging, C(2)D(2)(4+)→ D(+) + C(+) + C(+) + D(+).

Probing excited states dynamics in CO cations using few-cycle IR and EUV laser pulses

We have used few-cycle IR and EUV laser pulses in pump-probe arrangement to trace out the dissociation pathways in CO when exploded by strong laser fields. We present two preliminary sets of data of different pump pulses. In these sets, different excited state of CO cations are populated using (< 10 fs) IR, and EUV pulses respectively. We followed the time evolution of these states using the time-resolved Coulomb explosion imaging technique. We compare the time evolution of IR- and EUV-induced excited states by measuring the KER of the fragment ions as a function of the time delay between the pump and the IR probe pulse.

A combined experimental and theoretical study on realizing and using laser controlled torsion of molecules

It is demonstrated that strong laser pulses can introduce torsional motion in the axially chiral molecule 3,5-difluoro-3('),5(')-dibromobiphenyl. A nanosecond laser pulse spatially aligns the stereogenic carbon-carbon (C-C) bond axis allowing a perpendicularly polarized, intense femtosecond pulse to initiate torsional motion accompanied by a rotation about the fixed axis. We monitor the induced motion by femtosecond time-resolved Coulomb explosion imaging. Our theoretical analysis corroborates the experimental findings and on the basis of these results we discuss future applications of laser-induced torsion, viz., time-resolved studies of deracemization and laser controlled molecular junctions based on molecules with torsion.