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We present the simulation of the photochemical dynamics of cyclobutanone induced by the excitation of the 3s Rydberg state. For this purpose, we apply the complete active space self-consistent field method together with spin-orbit…

Chemical Physics · Physics 2024-01-15 Xincheng Miao , Kira Diemer , Roland Mitrić

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

We simulate the photodynamics of gas-phase cyclobutanone excited to the S$_2$ state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total C3+C2 photoproduct…

Chemical Physics · Physics 2024-07-23 Ericka Roy Miller , Sean J. Hoehn , Abhijith Kumar , Dehua Jiang , Shane M. Parker

In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photo-excitation to the S2…

Simulations of photochemical reaction dynamics have been a challenge to the theoretical chemistry community for some time. In an effort to determine the predictive character of current approaches, we predict the results of an upcoming…

Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining…

Chemical Physics · Physics 2024-02-16 Olivia Bennett , Antonia Freibert , K. Eryn Spinlove , Graham A. Worth

Owing to ring-strain, cyclic ketones exhibit complex excited-state dynamics with multiple competing photochemical channels active on the ultrafast timescale. While the excited-state dynamics of cyclobutanone after $\pi^{\ast}\leftarrow n$…

Chemical Physics · Physics 2024-02-15 Julien Eng , Conor Rankine , Thomas Penfold

Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet…

Chemical Physics · Physics 2024-05-28 Thomas V. Papineau , Denis Jacquemin , Morgane Vacher

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…

The comprehension of nonadiabatic dynamics in polyatomic systems relies heavily on the simultaneous advancements in theoretical and experimental domains. The gas-phase electron diffraction (GUED) technique has attracted widespread attention…

Chemical Physics · Physics 2024-02-15 Jiawei Peng , Hong Liu , Zhenggang Lan

To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strenghts. Twelve…

Dissociative chemisorption is a key process in hydrogen-metal surface chemistry, where nonadiabatic effects due to low-lying electron-hole-pair excitations may affect reaction outcomes. Molecular dynamics with electronic friction…

Chemical Physics · Physics 2025-05-26 Wojciech G. Stark , Connor L. Box , Matthias Sachs , Nils Hertl , Reinhard J. Maurer

We investigated the ultrafast structural dynamics of cyclobutanone following photoexcitation at $\lambda=200$ nm using gas-phase megaelectronvolt ultrafast electron diffraction. Our investigation complements the simulation studies of the…

We study the photoinduced chemical dynamics of cyclobutanone upon excitation at 200 nm to the 3s Rydberg state using MeV ultrafast electron diffraction (UED). We observe both the elastic scattering signal, which contains information about…

Chemical Physics · Physics 2025-06-30 Tianyu Wang , Hui Jiang , Cheng Jin , Xiao Zou , Pengfei Zhu , Tao Jiang , Feng He , Dao Xiang

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

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…

Chemical Physics · Physics 2016-07-27 Alexander Humeniuk , Roland Mitrić

We study the ultrafast time evolution of cyclobutanone excited to singlet n-->Rydberg state through XMS-CASPT2 nonadiabatic surface-hopping simulations. These dynamics predict relaxation to ground-state with a timescale of 822 +/- 45 fs…

Chemical Physics · Physics 2024-04-19 V. K. Jaiswal , F. Montorsi , F. Aleotti , F. Segatta , D. Keefer , S. Mukamel , A. Nenov , I. Conti , M. Garavelli

This work is part of a prediction challenge that invited theoretical/computational chemists to predict the photochemistry of cyclobutanone in the gas phase, excited at 200 nm by a laser pulse, and the expected signal that will be recorded…

The non-radiative electron-relaxation dynamics in C$_{60}$ molecule is studied after selective initial photoexcitations. The methodology includes nonadibabtic molecular simulation combined with time-dependent density functional theory (DFT)…

Atomic and Molecular Clusters · Physics 2023-06-29 Esam Ali , Mohamed El-Amine Madjet , Ruma De , Thomas Frauenheim , Himadri S. Chakraborty

Collisions of atoms and molecules with metal surfaces create electronic excitations in the metal, leading to nonadiabatic energy dissipation, inelastic scattering, and sticking. Mixed quantum-classical molecular dynamics simulation methods,…

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