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Ionization can serve as a universal probe of excited-state dynamics in molecules, such as internal conversion, dissociation, and isomerization. These processes are of fundamental importance to a wide array of dynamics in biology, chemistry, and physics. In recent years, there has been significant debate about the relative merits of strong-field ionization (SFI), which involves multiphoton absorption, versus weak-field ionization (WFI), where a single photon is absorbed, as probes of these dynamics. SFI is advantageous because it uses wavelengths that are relatively easy to generate, and one can always ionize the molecule with sufficient intensity. However, for SFI it is difficult to calculate observables, such as the time-dependent ion yield, since the calculation of the ionization dynamics including multiphoton processes is computationally expensive and difficult to carry out for many molecular geometries. WFI has the advantage that calculations of observables are tractable. However, the generation and implementation of the appropriate wavelengths (photon energies) can be challenging, and the fixed energy of the probe can lead to technical complications in following the dynamics from excited states back down to the ground state. Here we present a quantitative comparison of the two approaches for following the excited-state dynamics of two molecules, diiodomethane and uracil. The combination of internal conversion and dissociation in these molecules provides an ideal comparison of WFI and SFI as a probe. We compare the measurements with calculations of the dynamics. Our work indicates that while SFI and WFI provide qualitatively similar information about the excited-state dynamics, only WFI results can be compared quantitatively with present-day calculations.

This paper provides a detailed description of how to construct a pulsed atomic beam source [including a fast ionization gauge (FIG) for characterization] with a unique combination of characteristics. We include technical drawings for a real-time adjustable piezo electric actuated pulsed valve capable of generating a 11

We study strong-field dissociative molecular double ionization with momentum-resolved quadruple coincidence measurements, measuring the two electrons and two ionic fragments produced with a coincidence velocity map imaging apparatus. We contrast measurements for two different molecules. In one case, our measurements reveal anticorrelation in the momentum for the two electrons. In the other, we find no anticorrelation, indicating differences in the underlying ionization dynamics.

We study strong-field molecular ionization, with a focus on indirect ionization to dissociative excited ionic states. Indirect ionization, also known as post-ionization excitation, refers to the excitation of the molecular cation following ionization to a lower-lying state. We propose two possible mechanisms underlying indirect ionization: resonant transitions facilitated by nuclear dynamics and nonadiabatic transitions driven by the laser field off resonance. We compare them by measuring the dependence of the indirect ionization yield on pulse duration for cations with different electronic structures. Both experiments and simulations confirm the importance of nuclear dynamics in indirect ionization and indicate the presence of off-resonant nonadiabatic transitions.

Time-resolved measurements of strong-field molecular ionization are performed to measure the photoelectron spectrum as a function of pump-probe delay. The measurements allow one to follow the ionization dynamics and break them down into three steps, which include electronic excitation, internal conversion, and coupling to the continuum.

We demonstrate a single-detector velocity map imaging setup which is capable of rapidly switching between coincidence and non-coincidence measurements. By rapidly switching the extraction voltages on the electrostatic lenses, both electrons and ions can be collected in coincidence with a single detector. Using a fast camera as the 2D detector avoids the saturation problem associated with traditional delay line detectors and allows for easy transitions between coincidence and non-coincidence data collection modes. This is a major advantage in setting up a low-cost and versatile coincidence apparatus. We present both coincidence and non-coincidence measurements of strong field atomic and molecular ionization.

We perform time-resolved UV pump (4.77 eV) and VUV probe (7.94 eV) measurements of internal conversion of 1,3-cyclohexadiene (CHD). Our measurements reveal a substantial ionization of the ``hot'' ground state following internal conversion despite the fact that our probe photon energy is below the ionization potential (8.21 eV). With the aid of electronic structure calculations, we interpret our results in terms of vibrationally assisted below-threshold ionization, where vibrational energy is converted to electronic energy. The effect relies on both having vibrational modes which allow for this vibrational-electronic coupling and exciting these modes during the internal conversion. We contrast our measurements in CHD with another similar molecule, cis,cis-1,3-cyclooctadiene (cis,cis-COD), for which we do not see the effect.

We demonstrate a coincidence velocity map imaging apparatus equipped with a novel time stamping fast optical camera, Tpx3Cam, whose high sensitivity and ns timing resolution allow for simultaneous position and time-of-flight detection. This single detector design is simple, flexible and capable of highly differential measurements. We show detailed characterization of the camera and its application in strong field ionization experiments., Comment: 18 pages, 12 figures

We compare the excited state dynamics of diiodomethane (CH2I2) and bromoiodomethane (CH2BrI) using time resolved photoelectron spectroscopy. A 4.65 eV UV pump pulse launches a dissociative wave packet on excited states of both molecules and the ensuing dynamics are probed via photoionization using a 7.75 eV probe pulse. The resulting photoelectrons are measured with the velocity map imaging technique for each pump-probe delay. Our measurements highlight differences in the dynamics for the two molecules, which are interpreted with high-level ab initio molecular dynamics (trajectory surface hopping) calculations. Our analysis allows us to associate features in the photoelectron spectrum with different portions of the excited state wave packet represented by different trajectories. The excited state dynamics in bromoiodomethane are simple and can be described in terms of direct dissociation along the C–I coordinate, whereas the dynamics in diiodomethane involve internal conversion and motion along multiple dimensions.

We study the ultrafast relaxation dynamics of uracil excited to the first bright ππ* state (S2) by an ultrafast laser pulse in the deep ultraviolet (central wavelength λ0 = 260 nm). With a unique combination of strong field dissociative ionization measurements, state of the art strong field ionization calculations, and high level ab initio calculations of excited neutral and ionic states at critical points along the neutral potentials, we are able to gain a detailed picture of the relaxation dynamics of the molecule, which resolves earlier disagreements regarding measurements and calculations of the relaxation. © 2013 American Chemical Society.

We compare the time- and angle-dependent strong-field ionization yields of three molecules with very similar electronic structure. A pump pulse in the deep ultraviolet excites 1,3-cyclohexadiene, α-terpinene, and α-phellandrene to their first excited state. The latter two molecules are alkyl-substituted 1,3-cyclohexadiene systems. We then measure the strong-field ionization yield due to a near infrared probe pulse as a function of delay and angle between pump and probe polarization vectors. Ab initio electronic structure calculations allow us to associate the parent ion yields with removal of an electron from a LUMO orbital (occupied after excitation by the pump). Despite the fact that the LUMO orbitals for these molecules are very similar, the angle-dependent yields are very different, indicating that it is not the orbital shape alone which determines angle-dependent ionization yields.

We study strong-field molecular ionization as a function of pulse duration. Experimental measurements of the photoelectron yield for a number of molecules reveal competition between different ionization continua (cationic states) which depends strongly on pulse duration. Surprisingly, in the limit of short pulse duration, we find that a single ionic continuum dominates the yield, whereas multiple continua are produced for longer pulses. Using calculations which take vibrational dynamics into account, we interpret our results in terms of nuclear motion and non-adiabatic dynamics during the ionization process.

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.

We study strong-field molecular ionization using few- (four to ten) cycle laser pulses. Employing a supercontinuum light source, we are able to tune the optical laser wavelength (photon energy) over a range of $\ensuremath{\sim}200$ nm (500 meV). We measure the photoelectron spectrum for a series of different molecules as a function of laser intensity, frequency, and bandwidth and illustrate how the ionization dynamics vary with these parameters. We find that multiphoton resonances and nonadiabatic dynamics (internal conversion) play an important role and result in ionization to different ionic continua. Interestingly, while nuclear dynamics can be ``frozen'' for sufficiently short laser pulses, we find that resonances strongly influence the photoelectron spectrum and final cationic state of the molecule regardless of pulse duration---even for pulses that are less than four cycles in duration.

We investigate pathways for fragmentation in the uracil radical cation using ab initio electronic structure calculations. We focus on the main fragments produced in pump-probe dissociative ionization experiments. These are fragments with mass to charge ratios (m/z) of 69, 28, 41, and 42. Barriers to dissociation along the ground ionic surface are reported, which provide an estimate of the energetic requirements for the production of the main fragments. Direct and sequential fragmentation mechanisms have been analyzed, and it is concluded that sequential fragmentation after production of fragment with m/z 69 is the dominant mechanism for the production of the smaller fragments.

We demonstrate how the evolution of a bound vibrational wave packet can be controlled by a strong field laser pulse. We consider two different control schemes within the same molecule (CH(2)BrI): reshaping of the wave packet via strong field population transfer ("hole burning"), and redirecting its trajectory by dressing the potential energy surface on which the wave packet evolves ("photon locking"). Our measurements are compared with calculations using wave packet propagation on ab initio potential energy surfaces.

We present the application of ultrafast time- and mass-resolved ion yield laser spectroscopy in conjunction with ab initio electronic structure calculations to track molecular excited-state dynamics. We discuss how molecular fragment ions can be associated with conformations the molecule assumes during its relaxation, and how various features of the pump-probe signal for those fragments can be used to infer details of the excited-state dynamics. We present results for radiationless relaxation in DNA and RNA bases adenine, cytosine, and uracil in the gas phase, pumped near a one-photon resonance transition to an excited state, and probed via strong-field near-IR dissociative ionization.

We compare two-dimensional (2D) ultrafast Fourier transform spectroscopy measurements in the deep UV (262 nm) for adenine and uracil in solution. Both molecules show excited-state absorption on short time scales and ground-state bleaching extending for over 1 ps. While the 2D spectrum for uracil shows changes in the center of gravity during the first few hundred femtoseconds, the center of gravity of the 2D spectrum for adenine does not show similar changes. We discuss our results in light of ab initio electronic structure calculations.

This paper provides a detailed description of how to construct a pulsed atomic beam source [including a fast ionization gauge (FIG) for characterization] with a unique combination of characteristics. We include technical drawings for a real-time adjustable piezo electric actuated pulsed valve capable of generating a 11 μs duration pulse of gas at a repetition rate of >5 KHz, with a shot-to-shot stability of 0.6%, and maximum densities of 1015 particles/cm3. We also include details on how to construct a FIG, with a 4 μs rise time, to measure the pulse. We report a 3D density map of a supersonic expansion of helium gas with a speed ratio S = 46 and a calculated longitudinal temperature of 0.3 K. Finally, the results of a laser ionization test are provided in order to verify the performance of the pulsed valve in a typical experimental configuration.

We demonstrate the importance of considering the shape of field-dressed molecular orbitals in interpreting angle-dependent measures of strong-field ionization from excited states. Our calculations of angle-dependent ionization for three homologous polyatomic molecules with very similar valence orbitals show that one has to take into account the shape of the field-dressed orbitals rather than the field-free orbitals in order to rationalize the experimental measurements.

We investigate control over molecular fragmentation in the halogen substituted acetone 1,1-dibromo-3,3,3-trifluoroacetone using shaped ultrafast laser pulses. Following insight gained from closed-loop learning control experiments, further tests reveal that control over the CF3+/CHBr2+ ratio exploits a charge-transfer mechanism. We interpret the control in terms of adiabatic rapid passage.

Spectroscopic depth profiling of organic coatings is useful for characterizing the nature and spatial distribution of weather-induced aging on a coating system. Due to their highly heterogeneous compositions and general opacity, high-solids organic coatings can be extremely difficult to depth profile using established techniques. This work evaluates the feasibility of using femtosecond time-scale laser pulses as a method for preparing coating samples for the purpose of depth-resolved spectroscopic analysis. Samples were prepared by ablating square regions of various depths in military coating samples. Ablated regions were characterized morphologically using a custom scanning confocal profilometer and spectroscopically using Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS) and dispersive Raman spectroscopy. Depth profiles collected from ablated samples were compared with profiles of the same material collected using a cross-sectional transmission-mode FTIR technique. A threshold level was found, below which a compound-selective ablation process was observed. Additional ether cross-linking was found to occur at moderate/high energy levels. Material in the residual interaction volume showed indications of reconstituted urethane functionality.

We analyze the physical mechanisms underlying control over molecular fragmentation in a family of similar molecules using shaped ultrafast laser pulses. Our interpretation of the control mechanism in one molecule allows us to predict the nature and degree of control possible in the others. The predictions are verified and variations in the control are discussed. This study points to systematic behavior in chemical reactions of similar species driven by photonic reagents.

Using extremely broadband ultrafast near-infrared pulses, scientists have demonstrated simultaneous second-harmonic-generation, third-harmonic-generation and four-wave-mixing microscopy, enabling a range of different structures and functional groups in a biological sample to be imaged at once.

We study the relaxation dynamics of pyrrole after excitation with an 8 eV pump pulse to a state just 0.2 eV below the ionization potential using vacuum ultraviolet/ultraviolet pump probe spectroscopy. Our measurements in conjunction with electronic structure calculations indicate that pyrrole undergoes rapid internal conversion to the ground state in less than 300 fs. We find that internal conversion to the ground state dominates over dissociation.

We use ultrafast laser pulse shaping to discriminate between different pathways to multiple continua in strong-field molecular ionization. Shaping the laser pulse which ionizes the molecule allows us to control the photoelectron spectrum, which we interpret using a recently developed model of resonantly enhanced multiphoton ionization. Our measurements and calculations allow us to distinguish between a single intermediate resonance leading to multiple continua and multiple intermediate resonances each leading to a separate continuum.

We present a simple model for calculating strong field atomic and molecular ionization dominated by Freeman resonances. Our model combines multiphoton coupling between bound states, including dynamic Stark shifts, with coupling to a discretized continuum. The simplicity of the model allows us to interpret pulse shape dependent strong field ionization yields and to demonstrate the relevance of strong field atomic/molecular phase matching to ionization as well as bound state population transfer. Comparison with experimental measurements demonstrates that the calculations capture the essence of the pulse shape dependent ionization yields.

We study strong-field molecular ionization with shaped ultrafast laser pulses. We measure both photoions and photoelectrons as a function of laser pulse shape using a velocity map imaging spectrometer. We analyze correlations between photoelectrons and photoions as a function of photoelectron energy and ionic fragment mass-to-charge ratio. Our analysis focuses on resonant structures in the photoelectron spectrum known as Freeman resonances, and highlights both direct and indirect ionization to multiple states of the molecular cation.

An evolutionary learning algorithm in conjunction with an ultrafast optical pulse shaper was used to control vibrational motion in molecular gases at room temperature and high pressures. We demonstrate mode suppression and enhancement in sulfur hexafluoride and mode selective excitation in carbon dioxide. Analysis of optimized pulses discovered by the algorithm has allowed for an understanding of the control mechanism.

We have completely determined the amplitude and phase of a quantum wave packet. The wave packet was shaped using a programmable optical pulse. Phase information comes from analysis of covariant fluctuations due to interference between the wave packet and a well-characterized reference.

We have directly observed the motion of Rydberg wave packets of cesium in a static electric field through their ionization by half-cycle electromagnetic field pulses. Both Kepler orbital motion as well as angular motion, i.e., the periodic change in orbit ellipticity due to angular momentum evolution, can be clearly seen. The latter has never been directly observed, because conventional photoionization and two-pulse optical interferometry experiments are only sensitive to dynamics near the ion core and not when the wave packet has a high angular momentum.

We study correlations between neutral and ionic states in strong-field molecular ionization. We compare predictions based on Dyson orbital norms and quasistatic semiclassical tunneling theories (Keldysh and molecular orbital Ammosov-Delone-Krainov) with more detailed calculations of strong-field ionization which take into account (i)the Coulomb interaction between the outgoing continuum electron wave packet and the remaining bound electrons and (ii)electron-core interactions that cause distortions of the electronic continuum states during the ionization event. Our results highlight the prominence of electronic rearrangement effects in strong-field ionization with intense ultrafast laser pulses, where the outgoing continuum electron can cause electronic transitions in the parent ion. Calculations and measurements for excited uracil molecules reveal the breakdown of Keldysh-weighted Dyson norm predictions for ionization to different states of the molecular cation in the strong-field regime. © 2012 American Physical Society.

We use an acousto-optic modulator at the input to a two-dimensional, Fourier-domain pulse shaper to achieve built-in characterization of the output pulses with spectral interferometry. The device is capable of rapid switching between pulse shapes.

The extreme-ultraviolet (XUV) and strong-field valence ionization of cytosine and uracil is considered. We examine some simple estimates of the relative yields of the cation states populated following ionization and compare these to the results of a recently developed ab initio-type numerical model designed to compute strong-field ionization of molecules, the so-called time-dependent resolution in ionic states (TD-RIS) method. In analogy with one-photon XUV ionization, where the photoionization matrix elements can be related to the Dyson orbitals, we construct estimates for the yield of strong-field ionization (SFI) to different cation states based on the Dyson orbital norms and the Keldysh tunneling ionization rate. In the case of XUV ionization, the Dyson norms are shown to be good predictors of the relative cation yields when compared with the TD-RIS yields. The Dyson- and Keldysh-based models underestimate the yield to excited cation states in the case of SFI. The increased yield to the excited cation states in the TD-RIS results is attributed to the inclusion of multielectron effects and continuum structure not present in the simple models. The molecular Ammosov-Delone-Krainov (MO-ADK) method of calculating SFI is also considered. This later method is seen to agree more closely with the Dyson- and Keldysh-based estimates as it also fails to capture the multielectron effects and continuum structure included in the TD-RIS approach. ©2012 American Physical Society.

We use multiphoton quantum-control spectroscopy to discriminate between unbound and enzyme-bound NADH (reduced nicotinamide adenine dinucleotide) molecules in solution. Shaped ultrafast laser pulses are used to illuminate both forms of NADH, and the ratio of the fluorescence from the bound and unbound molecules for different pulse shapes allows us to measure binding without spectrally resolving the emitted fluorescence or relying on the absolute fluorescence yield. This permits determination of enzyme binding in situations where spectrally resolved measurements and absolute fluorescence yields are difficult to obtain, and makes the approach ideal for multiphoton microscopy with molecular discrimination.

We demonstrate strong-field ionization from multiple orbitals of excited-state uracil molecules. The molecules are excited to the first bright state by an ultrafast laser pulse in the deep ultraviolet and then ionized with a strong-field laser pulse in the near infrared during ultrafast relaxation back down to the ground state. We measure time- and angle-dependent ion yields for multiple fragments created by strong-field ionization, and interpret the temporally and angularly resolved yields via ab initio electronic structure calculations. We find that the angular distribution for the electron removed from the lowest unoccupied molecular orbital follows the symmetry of the molecular orbital, whereas ionization of the molecule by removing electrons from deeper bound orbitals is more complicated.

8 pags, 9 figs. -- PACS number(s): 33.15.−e, 33.20.−t, 33.80.Rv, We explore strong field molecular ionization with velocity map imaging of fragment ions produced by dissociation following ionization. Our measurements and ab initio electronic structure calculations allow us to identify various electronic states of the molecular cation populated during ionization, with multiple pathways to individual states highlighted by the pulse shape dependence. In addition, we show that relative populations can be reconstructed from our measurements. The results illustrate how strong field molecular ionization can be complicated by the presence and interaction of multiple cationic states during ionization. © 2011 American Physical Society., We gratefully acknowledge support from the National Science Foundation under Award No. 0854922, the Hungarian Academy of Sciences and Deutsche Forschungsgemeninschaft (Nr. 436 UNG 113/188/0-1), and the European COST Action CM0702.

We analyze the behavior of a four-state, two-path atomic interferometer driven by shaped ultrafast laser pulses. The laser pulses interact with atomic rubidium, exciting the atoms to the $5D$ state via two intermediate resonances (the $5{P}_{1/2}$ and $5{P}_{3/2}$). The relative phase of the two paths can be modified by applying a varying spectral phase at the wavelength corresponding to one of the resonant transitions for each pathway. We trace out the behavior of the system from the simplest case of weak-field excitation with resonant fields to strong-field excitation with a broadband source. Our measurements and analysis reveal that while interference is observed for all field strengths and spectral widths, the character of the interference changes substantially.

We demonstrate the creation of vibrational wave packets on multiple electronic states of a molecule via strong-field ionization. Furthermore, we show that the relative contribution of the different electronic states depends on the shape of the laser pulse which launches the wave packets.

Information was stored as quantum phase in an N -state Rydberg atom data register. One or more flipped states stored in an eight-state atomic wave packet could be retrieved in a single operation, in agreement with a recent proposal by Grover.

We demonstrate a phenomenon very similar to electromagnetically induced transparency using a shaped ultrafast laser pulse. Pulse shaping allows us to produce probe and coupling pulses with arbitrary intensities and time delays. The coupling Rabi frequency and probe bandwidth are both on the order of 1 THz, which is much larger than the natural or Doppler broadened linewidth of the probe transition. Important dynamics associated with a time-dependent coupling field are discussed.

Different molecules with nearly identical absorption spectra can be distinguished with the help of shaped laser pulses and adaptive algorithms.

We demonstrate the use of shaped ultrafast laser pulses in the deep ultraviolet to control the ring opening isomerization of 1,3-cyclohexadiene to form 1,3,5-hexatriene. The experiments are performed with a gas phase sample and the isomerization yield is probed with dissociative ionization driven by a time-delayed, intense infrared laser pulse. Differences in the electronic structure of the ions for the two isomers, as shown by ab initio calculations, result in very different fragmentation products following strong-field ionization. We find that a shaped pulse yields a approximately 37% increase in the isomerization over an unshaped laser pulse.

We show how wave functions with the same energy and probability distribution but different momenta have very different dissociation probabilities when two molecular potentials are strongly coupled by an intense laser field. Our measurements of dynamics in a molecular family, in conjunction with molecular structure and wave-packet calculations, highlight the role of the wave-packet momentum, or spatially varying phase, in the dynamics leading to dissociation. Phase-dependent dynamics are central to coherent control of laser driven chemistry.

We demonstrate a new method for coherent control of bond excitation in the strong field regime. We can selectively excite one or more Raman-active modes in a molecular liquid without the need for externally generated coherent sources separated by the Stokes frequency. The method employs excitation with an intense, ultrafast, shaped pulse in a learning control loop.

The ability to control the shape and motion of quantum states1,2 may lead to methods for bond-selective chemistry and novel quantum technologies, such as quantum computing. The classical coherence of laser light has been used to guide quantum systems into desired target states through interfering pathways3,4,5. These experiments used the control of target properties — such as fluorescence from a dye solution6, the current in a semiconductor7,8 or the dissociation fraction of an excited molecule9 — to infer control over the quantum state. Here we report a direct approach to coherent quantum control that allows us to actively manipulate the shape of an atomic electron's radial wavefunction. We use a computer-controlled laser to excite a coherent state in atomic caesium. The shape of the wavefunction is then measured10 and the information fed back into the laser control system, which reprograms the optical field. The process is iterated until the measured shape of the wavefunction matches that of a target wavepacket, established at the start of the experiment. We find that, using a variation of quantum holography11 to reconstruct the measured wavefunction, the quantum state can be reshaped to match the target within two iterations of the feedback loop.

The authors time resolve molecular motion in bound state, ionic potentials that leads to bond cleavage during the interaction with intense, ultrafast laser fields. Resonances in molecular ions play an important role in dissociative ionization with ultrafast laser fields, and the authors demonstrate how these resonances evolve in time to produce dissociation after initial strong-field ionization. Exploiting such dynamic resonances offers the possibility of controlled bond breaking and characterizing time-dependent molecular structure.

We demonstrate strong-field population inversion in a three-level system with single and multiphoton coupling between levels using a single shaped ultrafast laser pulse. Our interpretation of the pulse shape dependence illustrates the difference between sequential population transfer and adiabatic rapid passage in three-level systems with multiphoton coupling between levels.