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A semicalssical method based on surface-hopping techniques is developed to model the dynamics of radiative association with electronic transitions in arbitrary polyatomic systems. It can be proven that our method is an extension of the…

Chemical Physics · Physics 2017-10-11 Péter Szabó , Magnus Gustafsson

A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this…

Chemical Physics · Physics 2020-09-24 Zuxin Jin , Joseph E. Subotnik

The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…

Chemical Physics · Physics 2013-12-16 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang

Linear off-resonant X-ray Raman techniques are capable of detecting the ultrafast electronic coherences generated when a photoexcited wave packet passes through a conical intersection. A hybrid femtosecond or attosecond probe pulse is…

Chemical Physics · Physics 2022-11-07 Lorenzo Restaino , Deependra Jadoun , Markus Kowalewski

For years, theoretical calculations and scalable computer simulations have complemented ultrafast experiments as they offer the advantage to overcome experimental restrictions and have access to the whole dynamics. This synergy between…

Chemical Physics · Physics 2024-02-20 Patricia Vindel-Zandbergen , Jesús González-Vázquez

Attochemistry aims to exploit the properties of coherent electronic wavepackets excited via attosecond pulses, to control the formation of photoproducts. Such molecular processes can in principle be simulated with various nonadiabatic…

Chemical Physics · Physics 2024-05-28 Thierry Tran , Anthony Ferté , Morgane Vacher

We develop a density matrix formalism to describe coupled electron-nuclear dynamics. To this end we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a…

Chemical Physics · Physics 2020-09-07 Eugene Stolyarov , Alexander White , Dmitry Mozyrsky

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…

Chemical Physics · Physics 2015-07-20 Rami Gherib , Ilya G. Ryabinkin , Artur F. Izmaylov

Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV-Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different…

Chemical Physics · Physics 2017-03-29 Sebastian Mai , Philipp Marquetand , Leticia González

Rare nonadiabatic events play a central role in photochemistry but remain difficult to simulate because excited-state dynamics is computationally demanding and often stochastic. Here we introduce a deterministic and time-reversible…

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples…

Chemical Physics · Physics 2022-02-08 Patricia Vindel-Zandbergen , Spiridoula Matsika , Neepa T. Maitra

Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as…

Chemical Physics · Physics 2016-05-24 Alexander White , Sergei Tretiak , Dmitry Mozyrsky

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…

Quantum Physics · Physics 2024-01-30 Yuchen Wang , David A. Mazziotti

We introduce and analyze numerical companion matrix methods for the reconstruction of hypersurfaces with crossings from smooth interpolants given unordered or, without loss of generality, value-sorted data. The problem is motivated by the…

Numerical Analysis · Mathematics 2024-07-08 Timon S. Gutleb , Rhyan Barrett , Julia Westermayr , Christoph Ortner

Using the recently developed multistate mapping approach to surface hopping (multistate MASH) method combined with SA(3)-CASSCF(12,12)/aug-cc-pVDZ electronic structure calculations, the gas-phase isotropic ultrafast electron diffraction…

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…

Chemical Physics · Physics 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan

Nonstationary molecular states which contain electronic coherences can be impulsively created and manipulated by using recently-developed ultrashort optical and X-ray pulses via photoexcitation, photoionization and Auger processes. We…

Chemical Physics · Physics 2015-09-02 Konstantin E. Dorfman , Kochise Bennett , Shaul Mukamel

Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…

Numerical Analysis · Mathematics 2022-05-06 Zhenning Cai , Di Fang , Jianfeng Lu

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…

Quantum Physics · Physics 2023-10-18 Bing Gu

The rates and outcomes of virtually all photophysical and photochemical processes are determined by Conical Intersections. These are regions of degeneracy between electronic states on the nuclear landscape of molecules where electrons and…

Chemical Physics · Physics 2022-05-25 Daniel Keefer , Thomas Schnappinger , Regina de Vivie-Riedle , Shaul Mukamel