Ultrafast relaxation dynamics of uracil probed via strong field dissociative ionization.

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.

Neutral-ionic state correlations in strong-field molecular ionization.

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.

Fragmentation pathways in the uracil radical cation.

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.

Note: self-characterizing ultrafast pulse shaper for rapid pulse switching.

We use a high-efficiency acousto-optic modulator at the input to a two-dimensional Fourier-domain pulse shaper to achieve built-in characterization of the shaped output pulses. The acousto-optic modulator directs the beam to different vertical positions on a two-dimensional spatial light modulator, each of which can contain a different pulse shape. The undiffracted portion of the light serves as a reference beam for characterizing the shaped pulse via spectral interferometry. Pulse switching rates of 100 kHz can be achieved, making the device especially useful for quantum-control spectroscopy.

Two-dimensional fourier transform spectroscopy of adenine and uracil using shaped ultrafast laser pulses in the deep UV.

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.

Using shaped ultrafast laser pulses to detect enzyme binding.

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.

Distinguishing between relaxation pathways by combining dissociative ionization pump probe spectroscopy and ab initio calculations: a case study of cytosine.

We present a general method for tracking molecular relaxation along different pathways from an excited state down to the ground state. We follow the excited state dynamics of cytosine pumped near the S(0)-S(1) resonance using ultrafast laser pulses in the deep ultraviolet and probed with strong field near infrared pulses which ionize and dissociate the molecules. The fragment ions are detected via time of flight mass spectroscopy as a function of pump probe delay and probe pulse intensity. Our measurements reveal that different molecular fragments show different timescales, indicating that there are multiple relaxation pathways down to the ground state. We interpret our measurements with the help of ab initio electronic structure calculations of both the neutral molecule and the molecular cation for different conformations en route to relaxation back down to the ground state. Our measurements and calculations show passage through two seams of conical intersections between ground and excited states and demonstrate the ability of dissociative ionization pump probe measurements in conjunction with ab initio electronic structure calculations to track molecular relaxation through multiple pathways.

Combining dissociative ionization pump-probe spectroscopy and ab initio calculations to interpret dynamics and control through conical intersections.

Nonadiabatic processes play an important role in molecular dynamics, and understanding these processes better can help interpret and guide control over molecules. We are using high level electronic structure calculations in combination with intense, shaped, ultrafast laser pulses to study excited state dynamics in the nucleic acid bases, cytosine and uracil. These molecules have very short excited state lifetimes as they relax radiationless through conical intersections after absorption of UV radiation. The presence of more than one relaxation pathway provides the possibility to control which pathway can be involved in the dynamics. In our approach the molecules were excited using ultrafast laser pulses in the deep UV and then probed with strong field near infrared pulses which ionize and dissociate the molecules. Key to this approach is the fact that different fragments exhibit different dynamics and we can correlate these fragments, and their associated dynamics, to the various pathways involved in the neutral dynamics. Multiconfigurational electronic structure methods were used to calculate potential energy surfaces of the neutral and ionic states involved in the dynamics. Calculating mechanisms for fragmentation in the ion enables us to relate specific fragments to different neutral pathways, and use them as signatures to follow the dynamics. Possibilities for control are also discussed.

Exploring wavepacket dynamics behind strong-field momentum-dependent photodissociation in CH(2)BrI(+).

The ultrafast photodissociation dynamics of CH(2)BrI(+) into CH(2)Br(+) + I is studied using high level ab initio electronic structure calculations in conjunction with integration of the time-dependent Schrödinger equation and compared with measured pump-probe signals. These pump-probe measurements provide evidence for momentum-dependent dissociation, which is interpreted using two theoretical models. The first is based on DFT and TD-DFT calculations neglecting spin-orbit coupling, while the other, more rigorous model employs a larger number of coupled multi-configurational potentials obtained by means of CASSCF calculations. The latter model highlights the role of spin-orbit coupling between ionic electronic states as well as the effect of strong fields in the quantum dynamics including Stark-shifts and multi-photon excitation.

Two-dimensional ultrafast fourier transform spectroscopy in the deep ultraviolet.

We demonstrate two-dimensional ultrafast fourier transform spectroscopy in the deep ultraviolet (approximately 260 nm) using an acousto-optic modulator based pulse shaper. The use of a pulse shaper in the ultraviolet allows for rapid scanning, high phase (time) stability (approximately 0.017 rad) and phase cycling. We present measurements on the DNA nucleobase Adenine.

Shaped ultrafast laser pulses in the deep ultraviolet.

We use an acousto-optic pulse shaper to directly control the phase and amplitude of femtosecond laser pulses in the deep ultraviolet (~ 260 nm). The efficiency of the pulse shaper is 21% and the output pulse energy is 2.8muJ. We are currently using these pulses in molecular coherent control experiments.

Bichromatic, phase compensating interferometer based on prism pair compressors.

We present a bichromatic prism pair interferometer (BPPI) for controlling the delay between laser pulses of two different frequencies propagating collinearly in a single beam. The BPPI is especially useful when working with ultrafast laser pulses because it intrinsically allows for independent control over the second-order dispersion experienced by the differently colored pulses. We use this control to demonstrate successful precompensation for blue (lambda approximately 390 nm) and UV (lambda approximately 260 nm) pulses that pass through 2.2 cm of dispersive material after the interferometer. The BPPI is extremely flexible and works with all frequencies from the UV to the near-infrared. We demonstrate this by describing measurements made with BPPIs configured for three different combinations of central frequencies.