Circularly polarized light-induced potentials and the demise of excited states

Carrasco, Sebastián; Rogan, José; Valdivia, J. A.; Chang, Bong‐Soon; Malinovsky, Vladimir S.; Solá, Ignacio R.

doi:10.1039/d1cp04523g

Cited by 5 publications

(5 citation statements)

References 56 publications

(63 reference statements)

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“…The conditions for a LICI to emerge are simple: the coupling between electronic states must vanish and the laser has to be resonant with the energy differences between states . In our case, in which the orientation is taken as a parameter, there will be a LICI if V a ( R ) = V b ( R ) – ℏω 1 , V b ( R ) = V c ( R ) – ℏω 2 , and the laser propagates parallel to the TDM. − This case is somewhat trivial because in the molecular frame, a field propagating parallel to the TDM does not couple with matter. This, however, is a consequence of not treating rotation as a dynamical variable.…”

Section: Resultsmentioning

confidence: 96%

Floquet Engineering of a Diatomic Molecule through a Bichromatic Radiation Field

Barriga,

Foa Torres,

Cárdenas

2024

J. Chem. Theory Comput.

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We report on a theoretical study of a Cs 2 molecule illuminated by two lasers and show how this can result in novel quantum dynamics. We reveal that these interactions facilitate the bypass of the noncrossing rule, forming light-induced conical intersections and modifiable avoided crossings. Our findings show how laser field orientation and strength, along with initial phase differences, can control molecular-state transitions, especially on the micromotion scale. We also extensively discuss how the interaction of radiation with matter gives rise to the emergence of potential energy surfaces of hybrids of radiation and molecular states. This research advances a technique for manipulating photoassociation processes in Cs 2 molecules, offering potential new avenues in quantum control.

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Section: Resultsmentioning

confidence: 96%

Floquet Engineering of a Diatomic Molecule through a Bichromatic Radiation Field

Barriga,

Foa Torres,

Cárdenas

2024

J. Chem. Theory Comput.

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“…We consider a H 2 molecule with the H–H bond aligned along the x̂ direction. Such diatomic systems are often considered to be a platform for artificial control of nonadiabatic dynamics through light-matter interactions (e.g., light-induced conical intersections). − We assume the CPL field is propagating along the ẑ direction and is left-hand polarized ( ϵ = x̂ + i ŷ ) with frequency ℏω = 0.5 hartree and amplitude scriptE 0 = 10 − 3 atomic unit (au). To fit our model, we calculated the energies of the lowest two singlet eigenstate S 0 , S 1 for the H 2 molecule at the restricted Hartree–Fock and configuration interaction singles (RHF/CIS) level of theory with the 6-311G* basis set as a function of the bond length ( R ).…”

Section: Results: Numerical Demonstration Of Total Angular Momentum C...mentioning

confidence: 99%

Angular Momentum Transfer between a Molecular System and a Continuous Circularly Polarized Light Field within a Semiclassical Born–Oppenheimer Surface Hopping Framework

Bian,

Subotnik

2024

J. Chem. Theory Comput.

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We simulate semiclassically angular momentum transfer for a molecular system subject to a circularly polarized light (CPL) field either moving along a single Born−Oppenheimer (BO) surface or moving along multiple BO surfaces. Both sets of simulations are able to conserve the total angular momentum around the propagation direction of the CPL field, the former requiring a Berry force and the latter requiring a surface parametrized by both nuclear position and momentum (a socalled phase-space approach). Our results provide new insight into the nature of semiclassical nonadiabatic dynamics methods and further demonstrate the power of such methods to capture angular momentum transfer between different media, highlighting the need for accurate algorithms that conserve the total angular momentum.

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“…Therefore, no further approximations concerning the electronic structure of the molecule are required, as confirmed in Bayer et al (2020) . In our model, the electron dynamics is treated quantum mechanically, whereas the slower dynamics of the nuclei is treated classically, which is an established strategy to reduce the dimensionality of the calculation ( Carrasco et al, 2022) . Specifically, we model the vibrational nuclear dynamics by inserting a time-dependent function R = R ( t ) into the electronic potential

, which periodically modulates the potential along the internuclear axis.…”

Section: Physical Systemmentioning

confidence: 99%

Molecular Free Electron Vortices in Photoionization by Polarization-Tailored Ultrashort Laser Pulses

Bayer

Wollenhaupt

2022

Front. Chem.

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Atomic and molecular free electron vortices (FEVs), characterized by their spiral-shaped momentum distribution, have recently attracted a great deal of attention due to their varied shapes and their unusual topological properties. Shortly after their theoretical prediction by the single-photon ionization (SPI) of He atoms using pairs of counterrotating circularly polarized attosecond pulses, FEVs have been demonstrated experimentally by the multiphoton ionization (MPI) of alkali atoms using single-color and bichromatic circularly polarized femtosecond pulse sequences. Recently, we reported on the analysis of the experimental results employing a numerical model based on the ab initio solution of the time-dependent Schrödinger equation (TDSE) for a two-dimensional (2D) atom interacting with a polarization-shaped ultrashort laser field. Here, we apply the 2D TDSE model to study molecular FEVs created by SPI and MPI of a diatomic molecule using polarization-tailored single-color and bichromatic femtosecond pulse sequences. We investigate the influence of the coupled electron-nuclear dynamics on the vortex formation dynamics and discuss the effect of CEP- and rotational averaging on the photoelectron momentum distribution. By analyzing how the molecular structure and dynamics is imprinted in the photoelectron spirals, we explore the potential of molecular FEVs for ultrafast spectroscopy.

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Circularly polarized light-induced potentials and the demise of excited states

Abstract: In the presence of strong electric fields, the excited states of single-electron molecules and molecules with large transient dipoles become unstable because of anti-alignment, the rotation of the molecular axis...

Cited by 5 publications

References 56 publications

Floquet Engineering of a Diatomic Molecule through a Bichromatic Radiation Field

Floquet Engineering of a Diatomic Molecule through a Bichromatic Radiation Field

Angular Momentum Transfer between a Molecular System and a Continuous Circularly Polarized Light Field within a Semiclassical Born–Oppenheimer Surface Hopping Framework

Molecular Free Electron Vortices in Photoionization by Polarization-Tailored Ultrashort Laser Pulses

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