Generalized Velocity Sampling at a Transition State and Nonadiabatic Dynamics of Four-Membered Heterocyclic Peroxides DOI Creative Commons
Jian‐Ge Zhou, Yinan Shu,

Brianna Michaels

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3473 - 3482

Published: March 29, 2025

We propose the generalized initial velocity sampling algorithm at a transition state, in which total kinetic energy and extra positive along reaction coordinate have been introduced to improve accuracy efficiency of nonadiabatic dynamics simulation. This is very useful for chemical reactions with multiple states, e.g., two states thermolysis four-membered heterocyclic peroxides. The dependence chemiexcitation yields, dissociation times, other quantities on has investigated. By taking different CASPT2 corrections additional velocities into account, we found that resulting triplet quantum yield matches experimental result perfectly. In most ensembles, secondary primary intersystem crossing, i.e., first singlet excited state major direct production channel product trajectories.

Language: Английский

A MASH simulation of the photoexcited dynamics of cyclobutanone DOI Creative Commons
Joseph E. Lawrence, Imaad M. Ansari, Jonathan R. Mannouch

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(17)

Published: May 2, 2024

In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using mapping approach surface hopping (MASH). We consider first 500 fs relaxation following photoexcitation S2 state and predict corresponding time-resolved electron-diffraction signal that will be measured by planned experiment. 397 ab initio trajectories were obtained on fly with state-averaged complete active space self-consistent field (12,11) space. To obtain an estimate potential systematic error, 198 calculated aug-cc-pVDZ basis set 199 6-31+G* set. MASH is recently proposed independent trajectory method for simulating dynamics, originally derived two-state problems. As there are three relevant electronic states in this system, used newly developed multi-state generalization simulation: uncoupled spheres (unSMASH). This study, therefore, serves both as investigation photodissociation cyclobutanone, also demonstration applicability unSMASH simulations. line previous experimental studies, observe simulated dominated sets dissociation products, C3H6 + CO, C2H4 C2H2O, CH2 interpret our predicted terms key features associated pathways.

Language: Английский

Citations

8
A size-consistent multi-state mapping approach to surface hopping DOI
Joseph E. Lawrence, Jonathan R. Mannouch, Jeremy O. Richardson

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(24)

Published: June 28, 2024

We develop a multi-state generalization of the recently proposed mapping approach to surface hopping (MASH) for simulation electronically nonadiabatic dynamics. This new extends original MASH method be able treat systems with more than two electronic states. It differs from previous approaches in that it is size consistent and rigorously recovers two-state appropriate limits. demonstrate accuracy by applying series model which exact benchmark results are available, we find well suited photochemical relaxation processes.

Language: Английский

Citations

5
Solar brilliance unleashed: Improving efficiency above 31% of inorganic halide perovskite of Mg3AsX3 (X = F, Cl, Br, I) using DFT and SCAPS-1D DOI
Md. Azizur Rahman, Md. Ferdous Rahman, Md. Hafizur Rahman

et al.

Applied Physics Letters, Journal Year: 2024, Volume and Issue: 125(19)

Published: Nov. 4, 2024

This study investigates the structural, electronic, mechanical, and optical properties of perovskites Mg3AsX3 (X = F, Cl, Br, I) using DFT SCAPS-1D. The tolerance factor shows that these materials are thermodynamically stable. Furthermore, Mg3AsF3, Mg3AsCl3, Mg3AsBr3, Mg3AsI3 exhibit direct bandgaps 3.48, 2.06, 1.26, 0.265 eV, respectively, confirming their semiconducting nature. Mg3AsBr3 stands out for its ductility excellent properties, such as a high dielectric constant good conductivity, making it ideal solar cells. Under optimal conditions, FTO/WS2/Mg3AsBr3/Au structure demonstrated PCE 31.70%, with VOC 1.08 V, JSC 36.03 mA/cm2, fill (FF) 81.64%. These computational findings suggest Mg3AsBr3-based promising candidates developing highly efficient, lead-free, durable, cost-effective cells, offering valuable insights practical application in renewable energy technologies.

Language: Английский

Citations

5
Assessing the performance of coupled-trajectory schemes on full-dimensional two-state linear vibronic coupling models DOI
Peter Schürger, Lea M. Ibele, David Lauvergnat

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(10)

Published: March 14, 2025

We investigate the performance of coupled-trajectory methods for nonadiabatic molecular dynamics in simulating photodynamics 4-(dimethylamino)benzonitrile (DMABN) and fulvene, with electronic structure provided by linear vibrational coupling models. focus on mixed quantum-classical (CTMQC) algorithm (combined) Tully surface hopping [(C)CTTSH] comparison to independent-trajectory approaches, such as multi-trajectory Ehrenfest hopping. Our analysis includes not only populations but also additional nuclear properties position momentum space. For both DMABN recently developed CCTTSH successfully resolves internal inconsistencies Instead, we find that highlights a significant weakness CTMQC, which arises when trajectories remain long time vicinity region strong nonadiabaticity.

Language: Английский

Citations

0
Interexcited State Photophysics II: A Qualitative Excited State Dynamics Model from First-Principles DOI
Anjay Manian, Jessica M. de la Perrelle, Rohan J. Hudson

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

In Part I of this series [J. Chem. Theory Comput. 2023, 19(1), 271-292], a benchmarking study nuclear-electronic couplings was performed using 15 density functionals across two basis sets. From these, five functional and set combinations (data sets) yielded results that agreed with experiments for the S1 → S0 internal conversion (IC) rate in perylene. II, we use those data sets to calculate excited state dynamics perylene up second within theory (DFT) framework. Interexcited IC found be generally overestimated by 10 orders magnitude at ∼1020 s-1 best case S2 pathway. Probing methodology multireference method DFT overestimate coupling between states, CASSCF(8,8) overestimating 3 case. Therefore, applied faux-damping function, which reduced rates on singlet manifold 20 triplet manifold. With correction, constants compared well experimental value 302 ± 5 fs calculated work. Photoluminescence quantum yields (PLQYs) anti-Kasha (AKQYs) were calculated; PBE0/def2-TZVP most accurate PLQY AKQY (0.907 5.07 × 10-5, respectively). Although there is room refinement method, have shown qualitative prediction

Language: Английский

Citations

0
Ab initio spin-mapping non-adiabatic dynamics simulations of photochemistry DOI
Braden M. Weight, Arkajit Mandal, Deping Hu

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(8)

Published: Feb. 25, 2025

We perform on-the-fly non-adiabatic molecular dynamics simulations using the recently developed spin-mapping formalism. Two quantum approaches based on this mapping formalism, (i) fully linearized Spin-LSC and (ii) partially Spin-PLDM, are explored quasi-diabatic propagation scheme. have performed in four ab initio models for which benchmark multiple spawning (AIMS) data been published. find that spin-LSC previously reported symmetric quasi-classical (SQC) provide nearly equivalent population dynamics. While we expected more involved spin-PLDM method to superior accuracy compared other mapping-based approaches, SQC spin-LSC, found it with AIMS results. further explore underpinnings of correlation function by decomposing its N2 density matrix-focused initial conditions, where N is number states subsystem. Finally, an approximate form function, simplifies simulation reduces computational costs from N.

Language: Английский

Citations

0
Time-Reversible Implementation of MASH for Efficient Nonadiabatic Molecular Dynamics DOI Creative Commons

J. Amira Geuther,

Kasra Asnaashari, Jeremy O. Richardson

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which are only formally possible because deterministic nature underlying MASH equations motion. The new algorithms allow use either wave-function overlaps or coupling vectors propagate spin, encodes electronic state. For a given time-step, Δt, it is demonstrated that global error these methods O(Δt2) compared O(Δt) standard implementations. This allows larger time-steps be used desired tolerance, conversely, more accurate observables fixed value Δt. newly developed integrators thus provide further advantages method, demonstrating can implemented efficiently than other surface-hopping approaches, cannot construct due their stochastic nature.

Language: Английский

Citations

0
Generalized Velocity Sampling at a Transition State and Nonadiabatic Dynamics of Four-Membered Heterocyclic Peroxides DOI Creative Commons
Jian‐Ge Zhou, Yinan Shu,

Brianna Michaels

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3473 - 3482

Published: March 29, 2025

We propose the generalized initial velocity sampling algorithm at a transition state, in which total kinetic energy and extra positive along reaction coordinate have been introduced to improve accuracy efficiency of nonadiabatic dynamics simulation. This is very useful for chemical reactions with multiple states, e.g., two states thermolysis four-membered heterocyclic peroxides. The dependence chemiexcitation yields, dissociation times, other quantities on has investigated. By taking different CASPT2 corrections additional velocities into account, we found that resulting triplet quantum yield matches experimental result perfectly. In most ensembles, secondary primary intersystem crossing, i.e., first singlet excited state major direct production channel product trajectories.

Language: Английский

Citations

0