Related papers: Why do mixed quantum-classical methods describe sh…
Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional…
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…
We present a comprehensive computational framework for simulating nonadiabatic molecular dynamics with explicit inclusion of geometric phase (GP) effects. Our approach is based on a generalized two-level Hamiltonian model that can represent…
In molecular systems containing conical intersections (CIs), a nontrivial geometric phase (GP) appears in the nuclear and electronic wave-functions in the adiabatic representation. We study GP effects in nuclear dynamics of an N-dimensional…
We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all…
Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability…
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…
Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…
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…
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…
Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic…
An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…
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…
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…
This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral…
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…
The dynamics of an electronic two-level system coupled to an electromagnetic field are simulated explicitly for one and three dimensional systems through semiclassical propagation of the Maxwell-Liouville equations. We consider three…
Nonadiabatic dynamics around an avoid crossing or a conical intersection play a crucial role in the photoinduced processes of most polyatomic molecules. The present work shows that the topological phase in conical intersection makes the…
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…
In order to alleviate the computational costs of fully quantum nonadiabatic dynamics, we present a mixed quantum-classical (MQC) particle method based on the theory of Koopman wavefunctions. Although conventional MQC models often suffer…