On the multiphoton ionisation photoelectron spectra of phenol.

The phenol molecule is a prototype for non-adiabatic dynamics and the excited-state photochemistry of biomolecules. In this article, we report a joint theoretical and experimental investigation on the resonance enhanced multiphoton ionisation photoelectron (REMPI) spectra of the two lowest ionisation bands of phenol. The focus is on the theoretical interpretation of the measured spectra using quantum dynamics simulations. These were performed by numerically solving the time-dependent Schrödinger equation using the multi-layer variant of the multiconfiguration time-dependent Hartree algorithm together with a vibronic coupling Hamiltonian model. The ionising laser pulse is modelled explicitly within the ionisation continuum model to simulate experimental femtosecond 1+1 REMPI photoelectron spectra. These measured spectra are sensitive to very short lived electronically excited states, providing a rigorous benchmark for our theoretical methods. The match between experiment and theory allows for an interpretation of the features of the spectra at different wavelengths and shows that there are features due to both 'direct' and 'indirect' ionisation, resulting from non-resonant and resonant excitation by the pump pulse.

Quantum Interference Paves the Way for Long-Lived Electronic Coherences.

The creation and dynamical fate of a coherent superposition of electronic states generated in a polyatomic molecule by broadband ionization with extreme ultraviolet pulses is studied using the multiconfiguration time-dependent Hartree method together with an ionization continuum model Hamiltonian. The electronic coherence between the hole states usually lasts until the nuclear dynamics leads to decoherence. A key goal of attosecond science is to control the electronic motion and design laser control schemes to retain this coherence for longer timescales. Here, we investigate this possibility using time-delayed pulses and show how this opens up the prospect of coherent control of charge migration phenomenon.

Controlling the Ultrafast Dynamics of HD+ by the Carrier-Envelope Phases of an Ultrashort Laser Pulse: A Quasi-Classical Dynamics Study.

A theoretical study on the coupled electron-nuclear dynamics of HD+ molecular ions under ultrashort, intense laser pulses is performed by employing a well-established quasi-classical model. The influence of the laser carrier-envelope phase on various channel (H + D+, D + H+, and H+ + D+) probabilities is investigated at different laser field intensities. The carrier-envelope phase is found to govern the dissociation (H + D+ and D + H+) and Coulomb explosion (H+ + D+) channel probabilities. The kinetic energy release distributions of the fragments are also found to be sensitive to the carrier-envelope phase of the laser pulse. Our results are in agreement with the previously reported quantum dynamics studies and experiments.

Controlling Electron Dynamics with Carrier-Envelope Phases of a Laser Pulse.

A theoretical study on the ionization dynamics of carbon atom irradiated with a few-cycle, intense laser field is performed within a quasiclassical model to get mechanistic insights into an earlier reported carrier-envelope phase dependency of ionization probabilities of an atom [ Phys. Rev. Lett. 2013, 110, 083602]. The carrier-envelope phase of the laser pulse is found to govern the overall dynamics, reflecting its importance in controlling electronic motion. To understand the origin of this effect, individual trajectories were analyzed at a particular laser intensity. We found that a variation in the carrier-envelope phase affects the angle of ejection of the electrons and subsequently the attainment of the desired final state.

Non-resonant vibrational excitation of HOD and selective bond breaking.

This paper reports a time-dependent quantum mechanical wave packet study for bond-selective excitation and dissociation of HOD into the H + OD and D + OH channels in the first absorption band. Prior to excitation, the HOD molecule is randomly oriented with respect to a linearly polarized laser field and accurate static dipole moment and polarizability surfaces are included in the interaction potential. Vibrational excitation is obtained with intense, non-resonant 800 nm few-cycle excitation using dynamic Stark effect/impulsive Raman scattering. Dissociation is accomplished by another ultrashort vacuum ultraviolet-laser excitation. A laser control scheme is designed with a train of simple, non-resonant laser pulses in order to enhance the selectivity between the fragmentation channels. The effect of the carrier-envelope-phase of the ultrashort laser pulses is also investigated.

Coupled Electron-Nuclear Dynamics on H2+ within Time-Dependent Born-Oppenheimer Approximation.

Quantum dynamical behavior of H2+ in the presence of a linearly polarized, ultrashort, intense, infrared laser pulse has been studied by numerically solving the time-dependent Schrödinger equation with nuclear motion restricted in one-dimension along the direction of laser polarization and electronic motion in three-dimensions. On the basis of the time-dependent Born-Oppenheimer approximation, we have constructed time-dependent potentials for the ground electronic state (1sσg) of H2+. Subsequent nuclear dynamics is then carried out on these field-dressed potential energy surfaces, and the dissociation dynamics is investigated. Our analyses reveal that although the electronic longitudinal degree of freedom plays the major role in governing the dissociation dynamics, contributions from the electronic transverse degree of freedom should also have to be taken into account to obtain accurate results. Also, modeling electron-nuclei Coulomb interactions in a one-dimensional calculation with an artificially chosen constant softening parameter leads to a discrepancy with the exact results. Comparing our results with other quantum and classical dynamical studies showed a good agreement with exact results.

Effect of Vibrational Pre-Excitation on the Dissociation Dynamics of HOD(2+).

Preferential breaking of chemical bonds using few-cycle, intense laser pulse to obtain desired products offer a formidable challenge in understanding ultrafast chemical reactivity. In a recent study [J. Chem. Phys. 2015, 143, 244310], it was found that carrier-envelope phase influences the bond-selective fragmentation in HOD with up to 3-fold enhancement. We present a detailed theoretical study to understand the influence of initial vibrational states governing the dissociation dynamics. We have carried out a time-dependent quantum mechanical wave packet study on the ground electronic state (X̃ (3)B1) of HOD(2+). Analytical potential energy surface for the ground electronic states of both the neutral molecule and dication has been developed at multireference configuration interaction level of theory with aug-cc-pVQZ basis set. Branching ratio is computed from the accumulated flux in H(+) + OD(+) and D(+) + OH(+) dissociation channels. Our investigation demonstrate a strong dependency on the initial conditions, and thereby preferential cleavage of bonds can be achieved. We have also compared our results with experimental and other theoretical studies.

Coherent Phonon Dynamics in Plasmonic Gold Tetrahedral Nanoparticle Ensembles.

Coherent phonon modes supported by plasmonic nanoparticles offer prospective applications in chemical and biological sensing. Whereas the characterization of these phonon modes often requires single-particle measurements, synthetic routes to narrow size distributions of nanoparticles permit ensemble investigations. Recently, the synthesis of highly monodisperse gold tetrahedral nanoparticles with tunable edge lengths and corner sharpnesses has been developed. Herein, we characterize a size series of these nanoparticles in colloidal dispersion via transient absorption spectroscopy to examine their mechanical and plasmonic responses upon photoexcitation. Oscillations of transient absorption signals are observed in the plasmon resonance and correspond to the lowest-order radial breathing modes of the nanoparticles, the frequencies of which are affected by the edge length and truncation of the corners. Homogeneous quality factor values ranging from 24 to 34 are observed for the oscillations that convey potential utility in mass-sensing and plasmon-exciton-coupling photonics schemes. Finite-difference time domain and finite element analysis calculations establish specific optically relevant phonon modes.

Controlling Chemical Reactions with Laser Pulses.

One of the holy grails of contemporary science is to understand and manipulate chemical reactions to obtain desired products preferentially. To achieve this goal, chemists traditionally choose the correct starting materials and reaction conditions, but it often lacks selectivity and efficiency. A promising alternative is to design laser control schemes and apply them to guide and control chemical reactions. This mini-review attempts to provide theoretical insight into the laser-induced control of chemical reactions by highlighting some recent achievements, discussing the present challenges, and shedding some light on future prospects.

On Weak-Field (One-Photon) Coherent Control of Photoisomerization.

Photochemistry induced by phase-coherent laser light is an intriguing topic. The possibility of weak-field (one-photon) phase-only control of photoisomerization is controversial. Experimental studies on the weak-field coherent control of cis-trans isomerization have led to conflicting results. Here we address this issue by quantum dynamical calculations, focusing on a mechanism where different "phase-shaped" wave packets are quickly stabilized ("dumped") in the trans configuration because of prompt energy dissipation. We systematically investigate different relaxation rates with the system-bath dynamics described within the time-dependent Hartree approximation leading to a friction-type force. We find evidence for phase control of trans-isomer yields (about 5%) in this model with pure energy dissipation given sufficiently strong dampening.