Controlling vibrational cooling with Zero-Width Resonances: An adiabatic Floquet approach

In molecular photodissociation, some specific combinations of laser parameters (wavelength and intensity) lead to unexpected Zero-Width Resonances (ZWR), with in principle infinite lifetimes. Their interest in inducing basic quenching mechanisms have recently been devised in the laser control of vibrational cooling through filtration strategies [O. Atabek et al., Phys. Rev. A87, 031403(R) (2013)]. A full quantum adiabatic control theory based on the adiabatic Floquet Hamiltonian is developed to show how a laser pulse could be envelop-shaped and frequency-chirped so as to protect a given initial vibrational state against dissociation, taking advantage from its continuous transport on the corresponding ZWR, all along the pulse duration. As compared with previous control scenarios actually suffering from non-adiabatic contamination, drastically different and much more efficient filtration goals are achieved. A semiclassical analysis helps in finding and interpreting a complete map of ZWRs in the laser parameter plane. In addition, the choice of a given ZWR path, among the complete series identified by the semiclassical approach, amounts to be crucial for the cooling scheme, targeting a single vibrational state population left at the end of the pulse, while all others have almost completely decayed. The illustrative example, offering the potentiality to be transposed to other diatomics, is Na2 prepared by photoassociation in vibrationally hot but translationally and rotationally cold states.Comment: 15 pages, 14 figure

On-the-fly ab initio semiclassical evaluation of time-resolved electronic spectra

We present a methodology for computing vibrationally and time-resolved pump-probe spectra, which takes into account all vibrational degrees of freedom and is based on the combination of the thawed Gaussian approximation with on-the-fly ab initio evaluation of the electronic structure. The method is applied to the phenyl radical and compared with two more approximate approaches based on the global harmonic approximation - the global harmonic method expands both the ground- and excited-state potential energy surfaces to the second order about the corresponding minima, while the combined global harmonic/on-the-fly method retains the on-the-fly scheme for the excited-state wavepacket propagation. We also compare the spectra by considering their means and widths, and show analytically how these measures are related to the properties of the semiclassical wavepacket. We find that the combined approach is better than the global harmonic one in describing the vibrational structure, while the global harmonic approximation estimates better the overall means and widths of the spectra due to a partial cancellation of errors. Although the full-dimensional on-the-fly ab initio result seems to reflect the dynamics of only one mode, we show, by performing exact quantum calculations, that this simple structure cannot be recovered using a one-dimensional model. Yet, the agreement between the quantum and semiclassical spectra in this simple, but anharmonic model lends additional support for the full-dimensional ab initio thawed Gaussian calculation of the phenyl radical spectra. We conclude that the thawed Gaussian approximation provides a viable alternative to the expensive or unfeasible exact quantum calculations in cases, where low-dimensional models are not sufficiently accurate to represent the full system.Comment: Last 6 pages contain the Supplementary Materia

Application of the Mixed Time-averaging Semiclassical Initial Value Representation method to Complex Molecular Spectra

The recently introduced mixed time-averaging semiclassical initial value representation molecular dynamics method for spectroscopic calculations [M. Buchholz, F. Grossmann, and M. Ceotto, J. Chem. Phys. 144, 094102 (2016)] is applied to systems with up to 61 dimensions, ruled by a condensed phase Caldeira-Leggett model potential. By calculating the ground state as well as the first few excited states of the system Morse oscillator, changes of both the harmonic frequency and the anharmonicity are determined. The method faithfully reproduces blueshift and redshift effects and the importance of the counter term, as previously suggested by other methods. Differently from previous methods, the present semiclassical method does not take advantage of the specific form of the potential and it can represent a practical tool that opens the route to direct ab initio semiclassical simulation of condensed phase systems.Comment: 11 figure

Semiclassical instanton formulation of Marcus-Levich-Jortner theory

Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into a subsystem treated quantum-mechanically by Fermi's golden rule and a solvent bath treated by classical Marcus theory. As an extension of this idea, we here present a "reduced" semiclassical instanton theory, which is a multiscale method for simulating quantum tunnelling of the subsystem in molecular detail in the presence of a harmonic bath. We demonstrate that instanton theory is typically significantly more accurate than the cumulant expansion or the semiclassical Franck-Condon sum, which can give orders-of-magnitude errors and in general do not obey detailed balance. As opposed to MLJ theory, which is based on wavefunctions, instanton theory is based on path integrals and thus does not require solutions of the Schr\"odinger equation, nor even global knowledge of the ground- and excited-state potentials within the subsystem. It can thus be efficiently applied to complex, anharmonic multidimensional subsystems without making further approximations. In addition to predicting accurate rates, instanton theory gives a high level of insight into the reaction mechanism by locating the dominant tunnelling pathway as well as providing information on the reactant and product vibrational states involved in the reaction and the activation energy in the bath similarly to what would be found with MLJ theory.Comment: 21 pages, 4 figure

Theoretical study of charge exchange dynamics in He+^+ + NO collisions

We investigate the charge transfer mechanism in the collisions of helium ions on nitric oxide using a molecular description framework with consideration of the orientation of the projectile toward the target. The anisotropy of the collision process has been analysed in detail in connection with the non-adiabatic interactions around avoided crossings. Potential energy curves, radial and rotational coupling matrix elements have been determined by means of ab initio quantum chemical methods. The collision dynamics is performed in the [1.-25.] keV collision energy range using a semiclassical approach, and the total electron transfer cross sections are analysed with regard to available experimental data.Comment: 16 pages, 3 tables, 6 figure