A Single-Shot Technique for Measuring Broadband Two-Photon Absorption Spectra in Solution.

Applications involving two-photon activation, including two-photon fluorescence imaging, photodynamic therapy, and 3D data storage, require precise knowledge of the two-photon absorption (2PA) spectra of target chromophores. Broadband pump-probe spectroscopy using femtosecond laser pulses provides wavelength-dependent 2PA spectra with absolute cross sections, but the measurements are sometimes complicated by cross-phase modulation effects and dispersion of the broadband probe. Here, we introduce a single-shot approach that eliminates artifacts from cross-phase modulation and enables more rapid measurements by avoiding the need to scan the time delay between the pump and the probe pulses. The approach uses counterpropagating beams to automatically integrate over the full interaction between the two pulses as they cross. We demonstrate this single-shot approach for a common 2PA reference, coumarin 153 (C153), in three different solvents using the output from a Yb:KGW laser. This approach provides accurate 2PA cross sections that are more reliable and easier to obtain compared with scanning pump-probe methods using copropagating laser beams. The single-shot method for broadband two-photon absorption (BB-2PA) spectroscopy also has significant advantages compared with single-wavelength measurements, such as z-scan and two-photon fluorescence.

Broadband Two-Photon Absorption Spectroscopy with Stimulated Raman Scattering as an Internal Standard.

Two-photon absorption (2PA) spectroscopy provides valuable information about the nonlinear properties of molecules. In contrast with single-wavelength methods, broadband 2PA spectroscopy using a pump-probe approach gives a continuous 2PA spectrum across a wide range of transition energies without tuning the excitation laser. This contribution shows how stimulated Raman scattering from the solvent can be used as a convenient and robust internal standard for obtaining accurate absolute 2PA cross sections using the broadband approach. Stimulated Raman scattering has the same pump-probe overlap dependence as 2PA, thus eliminating the need to measure the intensity-dependent overlap of the pump and probe directly. Eliminating the overlap represents an important improvement because intensity profiles are typically the largest source of uncertainty in the measurement of absolute 2PA cross sections using any method. Raman scattering cross sections are a fundamental property of the solvent and therefore provide a universal standard that can be applied any time the 2PA and Raman signals are present within the same probe wavelength range. We demonstrate this approach using sample solutions of coumarin 153 in methanol, DMSO, and toluene, as well as fluorescein in water.

Photochemical Decarbonylation of Oxetanone and Azetidinone: Spectroscopy, Computational Models, and Synthetic Applications.

Photoexcitation of cyclic ketones leads to the expulsion of carbon monoxide and a mixture of products derived from diradical intermediates. Here we show that synthetic utility of this process is improved if strained heterocyclic ketones are used. Photochemistry of 3-oxetanone and N-Boc-3-azetidinone has not been previously described. Decarbonylation of these 4-membered rings proceeds through a step-wise Norrish type I cleavage of the C-C bond from the singlet excited state. Ylides derived from both compounds are high-energy species that are kinetically stable long enough to undergo [3+2] cycloaddition with a variety of alkenes and produce substituted tetrahydrofurans and pyrrolidines. The reaction has a sufficiently wide scope to produce scaffolds that were either previously inaccessible or difficult to synthesize, thereby providing experimental access to new chemical space.

Synthesis of Cycloheptatriene-Containing Azetidine Lactones.

We prepared a collection of complex cycloheptatriene-containing azetidine lactones by applying two key photochemical reactions: "aza-Yang" cyclization and Buchner carbene insertion into aromatic rings. While photolysis of phenacyl amines leads to a rapid charge transfer and elimination, we found that a simple protonation of the amine enables the formation of azetidinols as single diastereomers. We provide evidence, through ultrafast spectroscopy, for the electron transfer from free amines in the excited state. Further, we characterize the aza-Yang reaction by establishing the dependence of the initial reaction rates on the rates of photon absorption. An unanticipated change in reactivity in morpholine analogues is explained through interactions with the tosylate anion. The Buchner reaction proceeds with a slight preference for one diastereomer over the other, and successful reaction requires electron-donating carbene-stabilizing substituents. Overall, 16 compounds were prepared over seven steps. Guided by an increase in structural complexity, efforts such as this one extend the reach of chemists into unexplored chemical space and provide useful quantities of new compounds for studies focused on their properties.

Ultrafast Excited State Dynamics of Spatially Confined Organic Molecules.

This Feature Article highlights the role of spatial confinement in controlling the fundamental behavior of molecules. Select examples illustrate the value of using space as a tool to control and understand excited-state dynamics through a combination of ultrafast spectroscopy and conventional steady-state methods. Molecules of interest were confined within a closed molecular capsule, derived from a cavitand known as octa acid (OA), whose internal void space is sufficient to accommodate molecules as long as tetracene and as wide as pyrene. The free space, i.e., the space that is left following the occupation of the guest within the host, is shown to play a significant role in altering the behavior of guest molecules in the excited state. The results reported here suggest that in addition to weak interactions that are commonly emphasized in supramolecular chemistry, the extent of empty space (i.e., the remaining void space within the capsule) is important in controlling the excited-state behavior of confined molecules on ultrafast time scales. For example, the role of free space in controlling the excited-state dynamics of guest molecules is highlighted by probing the cis-trans isomerization of stilbenes and azobenzenes within the OA capsule. Isomerization of both types of molecule are slowed when they are confined within a small space, with encapsulated azobenzenes taking a different reaction pathway compared to that in solution upon excitation to S2. In addition to steric constraints, confinement of reactive molecules in a small space helps to override the need for diffusion to bring the reactants together, thus enabling the measurement of processes that occur faster than the time scale for diffusion. The advantages of reducing free space and confining reactive molecules are illustrated by recording unprecedented excimer emission from anthracene and by measuring ultrafast electron transfer rates across the organic molecular wall. By monitoring the translational motion of anthracene pairs in a restricted space, it has been possible to document the pathway undertaken by excited anthracene from inception to the formation of the excimer on the excited-state surface. Similarly, ultrafast electron transfer experiments pursued here have established that the process is not hindered by a molecular wall. Apparently, the electron can cross the OA capsule wall provided the donor and acceptor are in close proximity. Measurements on the ultrafast time scale provide crucial insights for each of the examples presented here, emphasizing the value of both "space" and "time" in controlling and understanding the dynamics of excited molecules.

Ultrafast Dynamics of a Molecular Switch from Resonance Raman Spectroscopy: Comparing Visible and UV Excitation.

Resonance Raman spectroscopy probes the ultrafast dynamics of a diarylethene (DAE) molecular switch following excitation into the first two optical absorption bands. Mode-specific resonance enhancements for Raman excitation at visible (750-560 nm) and near-UV (420-390 nm) wavelengths compared with the calculated and experimental off-resonance Raman spectrum at 785 nm reveal different Franck-Condon active vibrations for the two electronically excited states. The resonance enhancements at visible wavelengths are consistent with initial motion on the first excited-state that promotes the cycloreversion reaction, whereas the enhancements for excitation at near-UV wavelengths highlight motions involving conjugated backbone and phenyl ring stretching modes that are orthogonal to the reaction coordinate. The results support a mechanism involving rapid internal conversion from the higher-lying state followed by cycloreversion on the first excited state. These observations provide new information about the reactivity of DAE derivatives following excitation in the visible and near-UV.

Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch.

Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30 fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400 nm. Many of the modes that become enhanced in the 750 nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400 nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation.

Electronic Structure of Liquid Alkanes: A Representative Case of Liquid Hexanes and Cyclohexane Studied Using Polarization-Dependent Two-Photon Absorption Spectroscopy.

Two-photon absorption (2PA) spectra of liquid cyclohexane and hexanes are reported for the energy range 6.4-8.5 eV (177-145 nm), providing detailed information about their electronic structures in bulk liquid. Using a broadband pump-probe fashion, we measured the continuous 2PA spectra by simultaneous absorption of a 266 nm (4.6 eV) pump photon and one UV-vis probe photon from the white-light continuum (1.8-3.9 eV). Theoretical one-photon absorption (1PA) and 2PA cross sections of isolated gas phase molecules are computed by the equation of motion coupled-cluster method with single and double substitutions (EOM-CCSD) to substantiate the assignment of the experimental spectra, and the natural transition orbital (NTO) analysis provides visualization of the participating orbitals in a transition. Our analysis suggests that upon solvation transitions at the lowest excitation energy involving promotion of electron to the 3s Rydberg orbitals are blue-shifted (∼0.55 eV for cyclohexane and ∼0.18 eV for hexanes) to a greater extent as compared to those involving other Rydberg orbitals, which is similar to the behavior observed for water and alcohols. All other transitions experience negligible (cyclohexane) or minor red-shift by ∼0.15-0.2 eV (hexane) upon solvation. In both alkanes, the spectra are entirely dominated by Rydberg transitions: the most intense bands in 1PA and 2PA spectra are due to the excitation of electrons to the Rydberg "p" and "d" type orbitals, respectively, although one transition terminating in the 3s Rydberg has significant 2PA strength. This work demonstrates that the gas phase electronic transition properties in alkanes are not significantly altered upon solvation. In addition, electronic structure calculations using an isolated-molecule framework appear to provide a reasonable starting point for a semiquantitative picture for spectral assignment and also to analyze the solvatochromic shifts for liquid phase absorption spectra.

Absolute Cross Sections of Liquids from Broadband Stimulated Raman Scattering with Femtosecond and Picosecond Pulses.

Broadband stimulated Raman scattering (SRS) is often observed in applications that use nonlinear spectroscopy to probe the composition or dynamics of complex systems. Whether the SRS response is measured intentionally or unintentionally, as a background signal, the relative scattering intensities provide a quantitative measure of the population profile of target molecules. Solvent scattering is a valuable internal reference for determining absolute concentrations in these applications, but accurate cross sections have been reported for only a limited number of transitions in select solvents and were measured using spontaneous Raman scattering with narrowband continuous wave or nanosecond light sources. This work reports the measurement and analysis of absolute Raman scattering cross sections spanning the frequency range of 500-4000 cm-1 for cyclohexane, DMSO, acetonitrile, methanol, water, benzene, and toluene using broadband SRS with femtosecond and picosecond Raman pump pulses at 488 nm. Varying the duration of the Raman pump pulses from ∼80 fs to >1 ps confirms that the cross sections are independent of the spectral bandwidth across the range of ∼250 to <20 cm-1. The cross sections and depolarization ratios measured using broadband SRS agree with the limited number of previously reported values, after accounting for overlapping transitions in the lower-resolution femtosecond and picosecond spectra. The SRS cross sections reported here can be used with confidence as internal reference standards for a wide range of applications, including nonlinear spectroscopy and coherent microscopy measurements using ultrafast lasers.

Ultrafast Spectroscopy of [Mn(CO)3] Complexes: Tuning the Kinetics of Light-Driven CO Release and Solvent Binding.

Manganese tricarbonyl complexes are promising catalysts for CO2 reduction, but complexes in this family are often photosensitive and decompose rapidly upon exposure to visible light. In this report, synthetic and photochemical studies probe the initial steps of light-driven speciation for Mn(CO)3(Rbpy)Br complexes bearing a range of 4,4'-disubstituted 2,2'-bipyridyl ligands (Rbpy, where R = tBu, H, CF3, NO2). Transient absorption spectroscopy measurements for Mn(CO)3(Rbpy)Br coordination compounds with R = tBu, H, and CF3 in acetonitrile reveal ultrafast loss of a CO ligand on the femtosecond time scale, followed by solvent coordination on the picosecond time scale. The Mn(CO)3(NO2bpy)Br complex is unique among the four compounds in having a longer-lived excited state that does not undergo CO release or subsequent solvent coordination. The kinetics of photolysis and solvent coordination for light-sensitive complexes depend on the electronic properties of the disubstituted bipyridyl ligand. The results indicate that both metal-to-ligand charge-transfer (MLCT) and dissociative ligand-field (d-d) excited states play a role in the ultrafast photochemistry. Taken together, the findings suggest that more robust catalysts could be prepared with appropriately designed complexes that avoid crossing between the excited states that drive photochemical CO loss.

On the Discrepancy between Experimental and Calculated Raman Intensities for Conjugated Phenyl and Thiophene Derivatives.

Compared with experimental spectra, calculations for conjugated phenyl and thiophene oligomers tend to overestimate the ground state Raman intensities of higher-frequency vibrations (1200-1800 cm-1) relative to the intensities at lower frequencies (<1200 cm-1). The discrepancy was observed in previous benchmarking work that examined the method dependence of the calculated Raman spectra for a series of aromatic molecules. This paper further investigates the nature of the discrepancy by examining the role of anharmonic corrections and the dependence of the calculated Raman spectra on the inter-ring torsion angle for the representative molecules biphenyl (BP), 2-phenylthiophene (PT), and 2,2'-bithiophene (BT). Perturbative anharmonic corrections to the spectra calculated using density functional theory (DFT) provide only slightly better agreement with experiment. On the other hand, calculations at larger torsion angles give up to 30% improvement in the relative Raman intensities compared with the spectra calculated at the optimized geometries. The torsion-angle dependence of the Raman intensities is most pronounced for delocalized C-C and C-S stretching modes, and less pronounced for bending and ring distortion modes that do not involve inter-ring stretching. Higher-level calculations using the coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] method indicate that DFT underestimates the energy barrier for torsion isomerization at small angles, and it overestimates the barriers at large angles, thus predicting minimum geometries at torsion angles that are too small. Therefore, the results suggest that the discrepancy in relative Raman intensities may be related to an overestimation of inter-ring conjugation by DFT, which also tends to favor geometries that are too planar.

Femtosecond Stimulated Raman Scattering from Triplet Electronic States: Experimental and Theoretical Study of Resonance Enhancements.

Femtosecond stimulated Raman scattering (FSRS) is a spectroscopic technique that probes the structural dynamics of molecules. The technique typically relies on an electronic resonance condition to increase signal strength or enhance species selectivity, giving a Raman enhancement that is vibrational-mode-specific and depends on the character of the resonant electronic state. The resonance condition is complicated for molecules already in an excited electronic state and also for systems where multiple electronic states are resonant or nearly resonant with the Raman excitation energy, both of which are often the case for FSRS. This paper examines the excitation wavelength dependence of the FSRS spectrum for the lowest triplet state of 2-phenylthiophene (PT). Except for an overall increase of the signal strength due to the resonance condition, the relative intensities of most Raman bands are relatively insensitive to the excitation wavelength, and the spectrum is remarkably similar to the calculated off-resonance spectrum obtained by neglecting the resonance condition. On the other hand, calculated resonance Raman spectra using a gradient approximation to simulate the resonance condition correctly predict the excitation wavelength dependence for a few modes but overestimate the relative enhancement of others. The weak wavelength dependence of the triplet spectrum of PT contrasts the case of the singlet FSRS spectrum for the same molecule. We attribute this discrepancy to a combination of homogeneous broadening, overlapping TN ← T1 transitions, and possibly vibronic coupling among states in the triplet manifold. This work highlights important limitations in using standard approaches to simulate excited-state resonance Raman spectra.

Electronic Structure of Liquid Methanol and Ethanol from Polarization-Dependent Two-Photon Absorption Spectroscopy.

Two-photon absorption (2PA) spectra of liquid methanol and ethanol are reported for the energy range 7-10 eV from the first electronic excitation to close to the liquid-phase ionization potential. The spectra give detailed information on the electronic structures of these alcohols in the bulk liquid. The focus of this Article is to examine the electronic structure change compared with water on substitution of a hydrogen by an alkyl group. Continuous 2PA spectra are recorded in the broadband pump-probe fashion, with a fixed pump pulse in the UV region and a white-light continuum as a probe. Pump pulses of two different energies, 4.6 and 6.2 eV, are used to cover the spectral range up to 10 eV. In addition, theoretical 2PA cross sections for both molecules isolated in the gas phase are computed by the equation-of-motion coupled-cluster method with single and double substitutions (EOM-CCSD). These computational results are used to assign both the experimental 2PA and literature one-photon linear absorption spectra. The most intense spectral features are due to transitions to the Rydberg states, and the 2PA spectra are dominated by the totally symmetric 3pz ← 2pz transition in both alcohols. The experimental 2PA spectra are compared with the simulated 2PA spectra based on ab initio calculations that reveal a general blue shift of the excited transitions upon solvation. The effective 2PA thresholds in methanol and ethanol decrease to 6.9 eV compared with 7.8 eV for water. The analysis of the 2PA polarization ratio leads us to conclude that the excited states of ethanol deviate more markedly from water in the lower energy region compared with methanol. The polarization dependence of the 2PA spectra reveal the symmetries of the excited states within the measured energy range. Natural transition orbital calculations are performed to visualize the nature of the transitions and the orbitals participating during electronic excitation.

Ultrafast trans → cis Photoisomerization Dynamics of Alkyl-Substituted Stilbenes in a Supramolecular Capsule.

Ultrafast spectroscopy reveals the effects of confinement on the excited-state photoisomerization dynamics for a series of alkyl-substituted trans-stilbenes encapsulated in the hydrophobic cavity of an aqueous supramolecular organic host-guest complex. Compared with the solvated compounds, encapsulated trans-stilbenes have broader excited-state absorption spectra, excited-state lifetimes that are 3-4 times longer, and photoisomerization quantum yields that are 1.7-6.5 times lower in the restricted environment. The organic capsule disrupts the equilibrium structure and restricts torsional rotation around the central C═C double bond in the excited state, which is an important motion for the relaxation of trans-stilbene from S1 to S0. The location and identity of alkyl substituents play a significant role in determining the excited-state dynamics and photoisomerization quantum yields by tuning the relative crowding inside the capsule. The results are discussed in terms of distortions of the ground- and excited-state potential energy surfaces, including the topology of the S1-S0 conical intersection.

Probing Dynamics in Higher-Lying Electronic States with Resonance-Enhanced Femtosecond Stimulated Raman Spectroscopy.

Femtosecond stimulated Raman scattering (FSRS) measurements typically probe the structural dynamics of a molecule in the first electronically excited state, S1. While these measurements often rely on an electronic resonance condition to increase signal strength or enhance species selectivity, the effects of the resonance condition are usually neglected. However, mode-specific enhancements of the vibrational transitions in an FSRS spectrum contain detailed information about the resonant (upper) electronic state. Analogous to ground-state resonance Raman spectroscopy, the relative intensities of the Raman bands reveal displacements of the upper potential energy surface due to changes in the bonding pattern upon S n ← S1 electronic excitation, and therefore provide a sensitive probe of the ultrafast dynamics in the higher-lying state, S n. Raman gain profiles from the wavelength-dependent FSRS spectrum of the model compound 2,5-diphenylthiophene (DPT) reveal several modes with large displacement in the upper potential energy surface, including strong enhancement of a delocalized C-S-C stretching and ring deformation mode. The experimental results provide a benchmark for comparison with calculated spectra using time-dependent density functional theory (TD-DFT) and equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD), where the calculations are based on the time-dependent formalism for resonance Raman spectroscopy. The simulated spectra are obtained from S1-S n transition strengths and the energy gradients of the upper (S n) potential energy surfaces along the S1 normal mode coordinates. The experimental results provide a stringent test of the computational approach, and indicate important limitations based on the level of theory and basis set. This work provides a foundation for making more accurate assignments of resonance-enhanced excited-state Raman spectra, as well as extracting novel information about higher-lying excited states in the transient absorption spectrum of a molecule.

Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory.

Femtosecond stimulated Raman scattering (FSRS) probes the structural dynamics of molecules in electronically excited states by following the evolution of the vibrational spectrum. Interpreting the dynamics requires accurate assignments to connect the vibrational bands with specific nuclear motions of an excited molecule. However, the assignment of FSRS signals is often complicated by mode-specific resonance enhancement effects that are difficult to calculate for molecules in electronically excited states. We present benchmark results for a series of eight aryl-substituted thiophene derivatives to show that calculated off-resonance Raman spectra can be used to assign experimental bands on the basis of a comparison of structurally similar compounds and careful consideration of the resonance condition. Importantly, we show that direct comparison with the off-resonant calculations can lead to incorrect assignments of the experimental spectrum if the resonance condition is neglected. These results highlight the importance of resonance enhancement effects in assigning FSRS spectra.

Two-photon absorption spectroscopy of stilbene and phenanthrene: Excited-state analysis and comparison with ethylene and toluene.

Two-photon absorption (2PA) spectra of several prototypical molecules (ethylene, toluene, trans- and cis-stilbene, and phenanthrene) are computed using the equation-of-motion coupled-cluster method with single and double substitutions. The states giving rise to the largest 2PA cross sections are analyzed in terms of their orbital character and symmetry-based selection rules. The brightest 2PA transitions correspond to Rydberg-like states from fully symmetric irreducible representations. Symmetry selection rules dictate that totally symmetric transitions typically have the largest 2PA cross sections for an orientationally averaged sample when there is no resonance enhancement via one-photon accessible intermediate states. Transition dipole arguments suggest that the strongest transitions also involve the most delocalized orbitals, including Rydberg states, for which the relative transition intensities can be rationalized in terms of atomic selection rules. Analysis of the 2PA transitions provides a foundation for predicting relative 2PA cross sections of conjugated molecules based on simple symmetry and molecular orbital arguments.

Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment.

Two-photon absorption (2PA) spectroscopy provides complementary, and sometimes more detailed, information about the electronic structure of a molecule relative to one-photon absorption (1PA) spectroscopy. However, our understanding of the 2PA processes is rather limited due to technical difficulties in measuring experimental 2PA spectra and theoretical challenges in computing higher-order molecular properties. This paper examines the 2PA spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene by a combined experimental and theoretical approach. The broadband 2PA spectra of all three compounds are measured under identical conditions in order to facilitate a direct comparison of the absolute 2PA cross sections in the range 3.5-6.0 eV. For comparison, the theoretical 2PA cross sections are computed using the equation-of-motion coupled-cluster method with single and double substitutions. Simulated 2PA spectra based on the calculations reproduce the main features of the experimental spectra in solution, although the quantitative comparison is complicated by a number of uncertainties, including limitations of the theoretical model, vibronic structure, broadening of the experimental spectra, and solvent effects. The systematic comparison of experimental and theoretical spectra for this series of structurally similar compounds provides valuable insight into the nature of 2PA transitions in conjugated molecules. Notably, the orbital character and symmetry-based selection rules provide a foundation for interpreting the features of the experimental 2PA spectra in unprecedented detail.

Carrier-envelope-phase stabilized terawatt class laser at 1 kHz with a wavelength tunable option.

We demonstrate a chirped-pulse-amplified Ti:Sapphire laser system operating at 1 kHz, with 20 mJ pulse energy, 26 femtosecond pulse duration (0.77 terawatt), and excellent long term carrier-envelope-phase (CEP) stability. A new vibrational damping technique is implemented to significantly reduce vibrational noise on both the laser stretcher and compressor, thus enabling a single-shot CEP noise value of 250 mrad RMS over 1 hour and 300 mrad RMS over 9 hours. This is, to the best of our knowledge, the best long term CEP noise ever reported for any terawatt class laser. This laser is also used to pump a white-light-seeded optical parametric amplifier, producing 6 mJ of total energy in the signal and idler with 18 mJ of pumping energy. Due to preservation of the CEP in the white-light generated signal and passive CEP stability in the idler, this laser system promises synthesized laser pulses spanning multi-octaves of bandwidth at an unprecedented energy scale.

Cycloreversion dynamics of a photochromic molecular switch via one-photon and sequential two-photon excitation.

Ultrafast pump-probe (PP) and pump-repump-probe (PReP) measurements examine the ring-opening reaction of a photochromic molecular switch following excitation to the first and higher excited states. Sequential two-photon excitation is a sensitive probe of the excited-state dynamics, because the secondary excitation maps the progress along the S1 reaction coordinate onto the higher excited states of the molecule. In this contribution, secondary excitation at 800 nm accesses more reactive regions of the excited-state potential energy surfaces than are accessible with direct vertical excitation in the visible or UV. The quantum yield for cycloreversion increases by a factor of 3.5 ± 0.9 compared with one-photon excitation when the delay between the 500 nm pump and 800 nm repump laser pulses increases beyond ~100 fs, in contrast with a slower ~3 ps increase that was previously observed for one-color sequential excitation at 500 nm. The evolution of an excited-state absorption band reveals the dynamics of the higher-lying excited state for both one-photon excitation in the UV and sequential two-photon excitation. The spectroscopy and dynamics of the higher-lying excited state are similar for both excitation pathways, including a lifetime of ~100 fs. The complementary PP and PReP measurements provide a detailed picture of the ultrafast excited-state dynamics, including new insight on the role of excited states above S1 in controlling the photochemical cycloreversion reaction.