Related papers: Making peace with random phases: Ab initio conical…
Conical intersections are ubiquitous in polyatomic molecules and responsible for a wide range of phenomena in chemistry and physics. We introduce and implement a local diabatic representation for the correlated electron-nuclear dynamics…
Conical intersections are degeneracies between electronic states and are very common in nature. It has been found that they can also be created both by standing or by running laser waves. The latter are called light-induced conical…
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…
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 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…
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…
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…
Conical intersections constitute the conceptual bedrock of our working understanding of ultrafast, nonadiabatic processes within photochemistry (and photophysics). Accurate calculation of potential energy surfaces within the vicinity of…
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…
Assemblies of highly excited Rydberg atoms in an ultracold gas can be set into motion by a combination of van-der-Waals and resonant dipole-dipole interactions. Thereby, the collective electronic Rydberg state might change due to…
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…
In this work, we employ trajectory-based simulations to predict the electronic coherences created by nonadiabatic dynamics near conical intersections. The mapping approach to surface hopping (MASH) is compared with standard fewest-switches…
We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon…
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 present a framework for simulating relaxation dynamics through a conical intersection of an open quantum system that combines methods to approximate the motion of degrees of freedom with disparate time and energy scales. In the vicinity…
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…
Geometric phases play a crucial role in diverse fields. In chemistry they appear when a reaction path encircles an intersection between adiabatic potential energy surfaces and the molecular wavefunction experiences quantum-mechanical…
We consider a fully quadratic vibronic model Hamiltonian for studying photoinduced electronic transitions through conical intersections. Using a second order perturbative approximation for diabatic couplings we derive an analytical…
We consider an implementation of the adiabatic spin dynamics approach in a tight-binding description of the electronic structure. The adiabatic approximation for spin-degrees of freedom assumes that the faster electronic degrees of freedom…