Related papers: Local diabatic representation of conical intersect…
Ab initio modeling of conical intersection dynamics is crucial for various photochemical, photophysical, and biological processes. However, adiabatic electronic states obtained from electronic structure computations involve random phases,…
We develop and implement an exact conical intersection nonadiabatic wave packet dynamics method that combines the local diabatic representation, Strang splitting for the total molecular propagator, and discrete variable representation with…
The choice of the electronic representation in on-the-fly quantum dynamics is crucial. The adiabatic representation is appealing since adiabatic states are readily available from quantum chemistry packages. The nuclear wavepackets are then…
We explore the simulation of conical intersections (CIs) on quantum devices, setting the groundwork for potential applications in nonadiabatic quantum dynamics within molecular systems. The intersecting potential energy surfaces of…
Electronic wave-functions in the adiabatic representation acquire nontrivial geometric phases (GPs) when corresponding potential energy surfaces undergo conical intersection (CI). These GPs have profound effects on the nuclear quantum…
Conical intersections are common in molecular physics and photochemistry, and are often invoked to explain observed reaction products. A conical intersection can occur when an excited electronic potential energy surface intersects with the…
Nonadiabaticity, i.e., the effect of mixing electronic states by nuclear motion, is a central phenomenon in molecular science. The strongest nonadiabatic effects arise due to the presence of conical intersections of electronic energy…
Nonadiabatic effects appear due to avoided crossings or conical intersections that are either intrinsic properties in field-free space or induced by a classical laser field in a molecule. It was demonstrated that avoided crossings in…
On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…
Choosing an appropriate representation of the molecular Hamiltonian is one of the challenges faced by simulations of the nonadiabatic quantum dynamics around a conical intersection. The adiabatic, exact quasidiabatic, and strictly diabatic…
Conical intersections between electronic potential energy surfaces are paradigmatic for the study of non-adiabatic processes in the excited states of large molecules. However, since the corresponding dynamics occurs on a femtosecond…
One of the intriguing effects due to conical intersections is the geometric phase, manifested as destructive quantum interference in the nuclear probability distribution. However, whether such geometric phaseinduced interference can survive…
Adequate simulation of non-adiabatic dynamics through conical intersection requires account for a non-trivial geometric phase (GP) emerging in electronic and nuclear wave-functions in the adiabatic representation. Popular mixed…
Conical intersections are ubiquitous in chemistry and physics, often governing processes such as light harvesting, vision, photocatalysis, and chemical reactivity. They act as funnels between electronic states of molecules, allowing rapid…
The direct observation of non-adiabatic dynamics at conical intersections is a long-standing goal of molecular physics. Novel time-resolved spectroscopies have been proposed which are sensitive to electronic coherences induced by the…
A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…
Conical intersections (CIs) are seen as the main mediators of nonadiabatic transitions; yet, mixed quantum-classical (MQC) simulations rarely, if ever, sample geometries with exactly degenerate electronic energies. Here we show that this…
We present a means of studying rare reactive pathways in open quantum systems using Transition Path Theory and ensembles of quantum jump trajectories. This approach allows for elucidation of reactive paths for dissipative, nonadiabatic…
We demonstrate coherent control of motional dynamics in trapped Rydberg ions engineered to exhibit a conical intersection between adiabatic potential-energy surfaces. Using quantum optimal control, an optimally shaped electric field drives…
We provide a pedagogical approach to the problem of avoided crossings between electronic molecular curves and to diabatic and adiabatic transitions when the nuclei of a diatomic molecule move according to classical mechanics. For simplicity…