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The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the…

Computational Physics · Physics 2022-06-29 Jianhang Xu , Ruiyi Zhou , Zhen Tao , Christopher Malbon , Volker Blum , Sharon Hammes-Schiffer , Yosuke Kanai

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear…

Chemical Physics · Physics 2021-05-11 Diptarka Hait , Martin Head-Gordon

Orbital-optimized density functional theory (DFT) has emerged as an alternative to time-dependent (TD) DFT capable of describing difficult excited states with significant electron density redistribution, such as charge-transfer, Rydberg,…

Chemical Physics · Physics 2025-01-22 Hanh D. M. Pham , Rustam Z. Khaliullin

Nuclear quantum effects are essential for correctly describing hydrogen-rich materials at high pressures. Superconducting hydrides and ice are prime examples of such systems, requiring the inclusion of lattice anharmonicity and nuclear…

The time-dependent density functional theory (TDDFT) has been broadly used to investigate the excited-state properties of various molecular systems. However, the current TDDFT heavily relies on outcomes from the corresponding ground-state…

Chemical Physics · Physics 2020-09-02 Shu-Hao Yeh , Aaditya Manjanath , Yuan-Chung Cheng , Jeng-Da Chai , Chao-Ping Hsu

Nuclear quantum effects are important in a variety of chemical and biological processes. The constrained nuclear-electronic orbital density functional theory (cNEO-DFT) has been developed to include nuclear quantum effects in energy…

Chemical Physics · Physics 2021-09-20 Xi Xu , Yang Yang

This work presents the formalism and implementation of excited state nuclear forces within density functional linear response theory (TDDFT) using a plane wave basis set. An implicit differentiation technique is developed for computing…

Other Condensed Matter · Physics 2009-11-11 Nikos L. Doltsinis , D. S. Kosov

Accurate prediction of adiabatic $0$-$0$ excited-state energies is crucial for modeling molecular photophysical processes. Here, we benchmark computational strategies for evaluating excited-state energies and singlet-triplet gaps obtained…

Chemical Physics · Physics 2026-05-08 Amrita Bera , Atreyee Majumdar , Raghunathan Ramakrishnan

Proton transfer is central to many processes of chemical interest. The simulation of proton transfer dynamics requires the inclusion of nuclear quantum effects, such as zero-point energy, nuclear delocalization, and tunneling. Herein, we…

Chemical Physics · Physics 2026-03-19 Joseph A. Dickinson , Mathew Chow , Eno Paenurk , Sharon Hammes-Schiffer

Within the nuclear-electronic orbital (NEO) framework, the real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) approach enables the simulation of coupled electronic-nuclear dynamics. In this approach, the electrons and…

Chemical Physics · Physics 2023-03-22 Tao E. Li , Sharon Hammes-Schiffer

Nuclear quantum effects and non-Born--Oppenheimer effects play a vital role in many chemical and biological processes, motivating the incorporation of such effects into dynamical simulations. In real-time nuclear--electronic orbital…

Chemical Physics · Physics 2026-05-27 Nicholas J. Boyer , Sharon Hammes-Schiffer

The nuclear-electronic orbital (NEO) approach incorporates nuclear quantum effects into quantum chemistry calculations by treating specified nuclei quantum mechanically, equivalently to the electrons. Within the NEO framework, excited…

Chemical Physics · Physics 2025-03-19 Christopher L. Malbon , Sharon Hammes-Schiffer

Density functional theory (DFT) has emerged as one of the most versatile and lucrative approaches in electronic structure calculations of many-electron systems in past four decades. Here we give an account of the development of a…

Chemical Physics · Physics 2019-04-19 Abhisek Ghosal , Amlan K. Roy

Excited-state methods within the nuclear--electronic orbital (NEO) framework have the potential to capture vibrational, electronic, and vibronic transitions in a single calculation. In the NEO approach, specified nuclei, typically protons,…

Chemical Physics · Physics 2026-03-16 Jonathan H. Fetherolf , Fabijan Pavošević , Sharon Hammes-Schiffer

This chapter provides a basic introduction to excited-state extensions of density functional theory (DFT), including time-dependent (TD-)DFT in both its linear-response and its explicitly time-dependent formulations. As applied to the…

Chemical Physics · Physics 2023-05-02 John M. Herbert

The Born-Oppenheimer (BO) approximation is less accurate in the presence of a strong magnetic field than in the absence of a field. This is due to the complicated and unpredictable response of electronic structure to the field, especially…

Chemical Physics · Physics 2023-03-29 Tanner Culpitt , Laurens D. M. Peters , Erik I. Tellgren , Trygve Helgaker

We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method…

Chemical Physics · Physics 2024-04-23 Richard Einsele , Roland Mitrić

The performance of time-independent, orbital optimized calculations of excited states is assessed with respect to charge transfer excitations in organic molecules in comparison to the linear-response time-dependent density functional theory…

Chemical Physics · Physics 2024-05-22 Elli Selenius , Alec Elías Sigurdarson , Yorick L. A. Schmerwitz , Gianluca Levi

Accurately modeling photochemical reactions is difficult due to the presence of conical intersections and locally avoided crossings as well as the inherently multiconfigurational character of excited states. As such, one needs a multi-state…

Chemical Physics · Physics 2024-04-26 Matthew R. Hennefarth , Matthew R. Hermes , Donald G. Truhlar , Laura Gagliardi

Electronic structure calculation of atoms and molecules, in the past few decades has largely been dominated by density functional methods. This is primarily due to the fact that this can account for electron correlation effects in a…

Chemical Physics · Physics 2013-07-12 Amlan K. Roy
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