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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…

Chemical Physics · Physics 2024-09-26 Seonghoon Choi , Jiří Vaníček

The exact factorization approach has led to the development of new mixed quantum-classical methods for simulating coupled electron-ion dynamics. We compare their performance for dynamics when more than two electronic states are occupied at…

The thorough treatment of electron-lattice interactions from first principles is one of the main goals in condensed matter physics. While the commonly applied adiabatic Born-Oppenheimer approximation is sufficient for describing many…

Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of…

Chemical Physics · Physics 2016-08-03 Basile F. E. Curchod , Federica Agostini , E. K. U. Gross

While the treatment of conical intersections in molecular dynamics generally requires nonadiabatic approaches, the Born-Oppenheimer adiabatic approximation is still adopted as a valid alternative in certain circumstances. In the context of…

Chemical Physics · Physics 2020-09-16 Jonathan I. Rawlinson , Cesare Tronci

The exact factorization of the time-dependent electron-nuclear wavefunction has been employed successfully in the field of quantum molecular dynamics simulations for interpreting and simulating light-induced ultrafast processes. In this…

Chemical Physics · Physics 2021-09-29 Federica Agostini , E. K. U. Gross

Using the Multi-Reference Configuration Interaction method, the adiabatic potential energy surfaces of Li3 are computed. The two lowest electronic states are bound and exhibit a conical intersection. By fitting the calculated potential…

Chemical Physics · Physics 2014-09-15 Elham Nour Ghassemi , Jonas Larson , Asa Larson

We present a novel nonadiabatic perturbation theory (NAPT) for correlated systems of electrons and nuclei beyond the Born-Oppenheimer (BO) approximation. The essence of the method is to exploit the smallness of the electronic-to-nuclear…

Chemical Physics · Physics 2025-11-05 Matisse Wei-Yuan Tu , E. K. U. Gross

We investigate the exact wavefunction as a single product of electronic and nuclear wavefunction for a model conical intersection system. Exact factorized spiky potentials and nodeless nuclear wavefunctions are found. The exact factorized…

Quantum Physics · Physics 2015-06-17 Ying-Chih Chiang , Shachar Klaiman , Frank Otto , Lorenz S. Cederbaum

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

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…

We study the real-time dynamics of a two-dimensional Anderson--Hubbard model using nonequilibrium self-consistent perturbation theory within the second-Born approximation. When compared with exact diagonalization performed on small…

Disordered Systems and Neural Networks · Physics 2016-03-11 Yevgeny Bar Lev , David R. Reichman

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…

Quantum Physics · Physics 2025-09-16 Abdessamad Belfakir , Yousra Bouasria , Herschel Rabitz , Ahmed Ratnani

This Review is devoted to the presentation of the exact factorization as a framework employed to study a variety of quantum-mechanical many-body problems. Since its original formulation in the 70s, the main applications of the exact…

Chemical Physics · Physics 2026-03-02 Peter Schürger , Sara Giarrusso , Federica Agostini

The global many-electron wave function overlap matrix accounts for all effects beyond the Born-Oppenheimer approximation in the discrete variable local diabatic representation, a numerically exact framework for modeling nonadiabatic conical…

Chemical Physics · Physics 2025-01-10 Yujuan Xie , Bing Gu

The adiabatic approximation is a natural approach for the description of phenomena induced by low frequency laser radiation because the ratio of the laser frequency to the characteristic frequency of an atom or a molecule is a small…

Atomic Physics · Physics 2010-12-27 Denys Bondar

Diabatization of the molecular Hamiltonian is a standard approach to removing the singularities of nonadiabatic couplings at conical intersections of adiabatic potential energy surfaces. In general, it is impossible to eliminate the…

Chemical Physics · Physics 2021-03-26 Seonghoon Choi , Jiří Vaníček

The evolution of a system induced by counter-diabatic driving mimics the adiabatic dynamics without the requirement of slow driving. Engineering it involves diagonalizing the instantaneous Hamiltonian of the system and results in the need…

Quantum Physics · Physics 2013-09-05 Adolfo del Campo

By analyzing an exactly solvable model in the second quantized formulation which allows a unified treatment of adiabatic and non-adiabatic geometric phases, it is shown that the topology of the adiabatic Berry's phase, which is…

Quantum Physics · Physics 2017-08-23 Kazuo Fujikawa

We discuss two different methods of obtaining ``effective $2 \times 2$ Hamiltonians'' of the electromagnetic interaction which include relativistic corrections. One is the standard Foldy--Wouthuysen transformation which we compare with the…

Nuclear Theory · Physics 2009-10-22 S. Scherer , G. I. Poulis , H. W. Fearing
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