Po-Yuan Cheng

Disentangling intrinsic ultrafast excited-state dynamics of cytosine tautomers.

Gas-phase ultrafast excited-state dynamics of cytosine, 1-methylcytosine, and 5-fluorocytosine were investigated in molecular beams using femtosecond pump-probe photoionization spectroscopy to identify the intrinsic dynamics of the major cytosine tautomers. The results indicate that, upon photoexcitation in the first absorption band, the cytosine enol tautomer exhibits a significantly longer excited-state lifetime than its keto and imino counterparts. The initially excited states of the cytosine keto and imino tautomers decay with sub-picosecond dynamics for excitation wavelengths shorter than 300 nm, whereas that of the cytosine enol tautomer decays with time constants ranging from 3 to 45 ps for excitation between 260 and 285 nm.

Ultrafast dynamics of gas-phase excited-state intramolecular proton transfer in 1-hydroxy-2-acetonaphthone

Abstract The excited-state dynamics of 1-hydroxy-2-acetonaphthone (HAN) was studied in the gas phase using femtosecond time-resolved multiphoton ionization spectroscopy. Following femtosecond excitation to its S 1 state, HAN was found to exhibit a biexponential decay behavior which can be consistently interpreted in terms of rapid excited-state intramolecular proton transfer (ESIPT) followed by other slower decay channels. The results revealed that ESIPT in HAN (S 1 ) occurs in ∼60–85 ps in the energy range studied and suggested the existence of an energy barrier to tautomerization.

Femtosecond pump-probe photoionization-photofragmentation spectroscopy: Photoionization-induced twisting and coherent vibrational motion of azobenzene cation

We report studies of ultrafast dynamics of azobenzene cation using femtosecond photoionization-photofragmentation spectroscopy. In our experiments, a femtosecond pump pulse first produces an ensemble of azobenzene cations via photoionization of the neutrals. A delayed probe pulse then brings the evolving ionic system to excited states that ultimately undergo ion fragmentation. The dynamics is followed by monitoring either the parent-ion depletion or fragment-ion formation as a function of the pump-probe delay time. The observed transients for azobenzene cation are characterized by a constant ion depletion modulated by a rapidly damped oscillatory signal with a period of about 1 ps. Theoretical calculations suggest that the oscillation arises from a vibration motion along the twisting inversion coordinate involving displacements in CNNC and phenyl-ring torsions. The oscillation is damped rapidly with a time constant of about 1.2 ps, suggesting that energy dissipation from the active mode to bath modes takes place in this time scale.

Ultrafast time-resolved broadband fluorescence studies of the benzene-tetracyanoethylene complex: solvation, vibrational relaxation, and charge recombination dynamics.

The charge-transfer (CT) state relaxation dynamics of the benzene-tetracyanoethylene (BZ-TCNE) complex was studied with broadband ultrafast time-resolved fluorescence spectroscopy implemented by optical Kerr gating in three solvents of different polarities. The CT state of the BZ-TCNE complex is reached via femtosecond laser excitation, and the subsequent temporal evolutions of the fluorescence spectra were measured. Analyses of various time-dependent spectral properties revealed rapid relaxations along solvent and vibrational coordinates in competition with charge recombination (CR). By comparing the results in solvents of different polarities, we partially separated solvation and vibrational relaxation dynamics and explored the solvent-dependent CR dynamics. Time-dependent dynamic fluorescence Stokes shift (TDFSS) measurements unveiled the solvation and vibrational relaxation contributions to the observed spectral relaxation. The biphasic and slow time scales of the vibrational contributions identified in TDFSS suggested nonstatistical and hindered intramolecular vibrational-energy redistribution that can be attributed to the unique structural properties of EDA complexes. The slowest spectral relaxation of 10-15 ps identified in TDFSS was ascribed to relaxation of the BZ(+)-TCNE(-) intermolecular vibrations, which is equivalent to a structural relaxation from the initial Franck-Condon configuration to the equilibrium CT-state structure. The time scales of vibrational relaxation indicate that a fraction of the CT-state population undergoes CR reactions before complete vibrational/structural equilibrium is achieved. In carbon tetrachloride, a nonexponential temporal profile was observed and attributed to vibrational nonequilibrium CR. In dichloromethane, polar solvation greatly accelerates CR reactions, and a slower reaction-field-induced structural relaxation gives rise to a pronounced biexponential decay. The equilibrium CR time constants of the BZ-TCNE CT state are 29 ps, 150 ps, and 68 ps in dichloromethane, carbon tetrachloride, and cyclohexane, respectively.

Femtosecond probing of photodissociation dynamics in acyl cyanides

The photodissociation of two acyl cyanide compounds, R–C(O)–CN, where R=methyl and tert-butyl groups, has been investigated using femtosecond time-resolved laser-induced fluorescence (LIF) spectroscopy. Both compounds were excited by two-photon excitation at a total energy of ∼6.4 eV and the formation of the free CN(X) radical products was probed in real time by monitoring the CN X→B LIF signal. The results revealed that the temporal evolution of the CN(X) formation can be well characterized by delayed biexponential rise functions with time constants in the picosecond time scale, indicating that the dissociation occurs via a complex-mode mechanism. We proposed a dissociation mechanism involving two discernable stages to account for the observed temporal behaviors as well as previous photofragment translational spectroscopic results reported by other groups. Our analyses suggested that the selectivity between the C–CN and C–R bond cleavage is determined by the competition between the adiabatic and nonadiab...

Unraveling Complex Three-Body Photodissociation Dynamics of Dimethyl Sulfoxide: A Femtosecond Time-Resolved Spectroscopic Study

Photodissociation of dimethyl sulfoxide at 200 nm has been studied using femtosecond time-resolved spectroscopy. The temporal evolutions of the initial state, intermediates, and products (CH3 and SO) were measured by means of fs pump-probe mass-selected multiphoton ionization and laser-induced fluorescence. Femtosecond time-resolved photofragment translational spectroscopy was also employed to measure the CH3 product kinetic energy distributions as a function of reaction time. The ionization experiments revealed that there are at least three major CH3 product components, whereas the fluorescence experiments indicated that two SO product components are present. The combination of experimental and theoretical results suggested a complex multichannel mechanism involving both concerted and stepwise three-body dissociation pathways.

Microhydration Effects on the Ultrafast Photodynamics of Cytosine: Evidences for a Possible Hydration-Site Dependence.

Ultrafast excited-state deactivation dynamics of small cytosine (Cy) and 1-methylcytosine (1mCy) microhydrates, Cy⋅(H2O)1-3 and 1mCy⋅(H2O)1,2, produced in a supersonic expansion have been studied by mass-selected femtosecond pump-probe photoionization spectroscopy at about 267 nm excitation. The seeded supersonic expansion of Ar/H2O gas mixtures allowed an extensive structural relaxation of Cy and 1mCy microhydrates to low-energy isomers. With the aid of electronic structure calculations, we assigned the observed ultrafast dynamics to the dominant microhydrate isomers of the amino-keto tautomer of Cy and 1mCy. Excited-state lifetimes of Cy⋅(H2O)1-3 measured here are 0.2-0.5 ps. Comparisons of the Cy⋅H2O and 1mCy⋅H2O transients suggest that monohydration at the amino Watson-Crick site induces a substantially stronger effect than at the sugar-edge site in accelerating excited-state deactivation of Cy.

Communication: Ultrafast time-resolved ion photofragmentation spectroscopy of photoionization-induced proton transfer in phenol-ammonia complex

Photoionization-induced proton transfer (PT) in phenol-ammonia (PhOH-NH3) complex has been studied using ultrafast time-resolved ion photofragmentation spectroscopy. Neutral PhOH-NH3 complexes prepared in a free jet are photoionized by femtosecond [1+1] resonance-enhanced multiphoton ionization via the S1 state, and the subsequent dynamics occurring in the cations is probed by delayed pulses that result in ion fragmentation. The observed temporal evolutions of the photofragmentation spectra are consistent with an intracomplex PT reaction. The experiments revealed that PT in [PhOH-NH3](+) cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ~70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the reaction may take a much longer time scale to complete.

Gas-phase femtosecond transient absorption spectroscopy

A setup for measuring femtosecond transient absorption in the gas phase is reported. The apparatus is based on a 1kHz amplified Ti:sapphire laser system and measures gas-phase transient absorption using a shot-to-shot normalization scheme with background subtraction. We have used this setup to examine the wave packet dynamics of the I2 B state in the vapor phase as a benchmark. The results are consistent with those reported by other groups using indirect transient absorption techniques.

Ultrafast photodissociation dynamics of cyanobenzene near the ionization threshold

Abstract The photodissociation of cyanobenzene (C 6 H 5 CN) at a high energy of ∼9.6 eV near the ionization threshold has been investigated using femtosecond time-resolved laser-induced fluorescence (LIF) spectroscopy. Cyanobenzene molecules were excited by three-photon excitation at 388.6 nm and the temporal evolution of the free CN(X) fragment formation was probed in real time by monitoring the CN X → B LIF signal. The results revealed that the CN(X) products are formed on three very different timescales, suggesting that the dissociation proceeds through at least three dissociation pathways at such a high energy.