6 research outputs found
Ab Initio Molecular Cavity Quantum Electrodynamics Simulations Using Machine Learning Models
We present a mixed quantum-classical simulation of polariton
dynamics
for molecule–cavity hybrid systems. In particular, we treat
the coupled electronic–photonic degrees of freedom (DOFs) as
the quantum subsystem and the nuclear DOFs as the classical subsystem
and use the trajectory surface hopping approach to simulate non-adiabatic
dynamics among the polariton states due to the coupled motion of nuclei.
We use the accurate nuclear gradient expression derived from the Pauli–Fierz
quantum electrodynamics Hamiltonian without making further approximations.
The energies, gradients, and derivative couplings of the molecular
systems are obtained from the on-the-fly simulations at the level
of complete active space self-consistent field (CASSCF), which are
used to compute the polariton energies and nuclear gradients. The
derivatives of dipoles are also necessary ingredients in the polariton
nuclear gradient expression but are often not readily available in
electronic structure methods. To address this challenge, we use a
machine learning model with the Kernel ridge regression method to
construct the dipoles and further obtain their derivatives, at the
same level as the CASSCF theory. The cavity loss process is modeled
with the Lindblad jump superoperator on the reduced density of the
electronic–photonic quantum subsystem. We investigate the azomethane
molecule and its photoinduced isomerization dynamics inside the cavity.
Our results show the accuracy of the machine-learned dipoles and their
usage in simulating polariton dynamics. Our polariton dynamics results
also demonstrate the isomerization reaction of azomethane can be effectively
tuned by coupling to an optical cavity and by changing the light–matter
coupling strength and the cavity loss rate
Analysis of the Geometrical Evolution in On-the-Fly Surface-Hopping Nonadiabatic Dynamics with Machine Learning Dimensionality Reduction Approaches: Classical Multidimensional Scaling and Isometric Feature Mapping
On-the-fly trajectory-based
nonadiabatic dynamics simulation has
become an important approach to study ultrafast photochemical and
photophysical processes in recent years. Because a large number of
trajectories are generated from the dynamics simulation of polyatomic
molecular systems with many degrees of freedom, the analysis of simulation
results often suffers from the large amount of high-dimensional data.
It is very challenging but meaningful to find dominating active coordinates
from very complicated molecular motions. Dimensionality reduction
techniques provide ideal tools to realize this purpose. We apply two
dimensionality reduction approaches (classical multidimensional scaling
and isometric feature mapping) to analyze the results of the on-the-fly
surface-hopping nonadiabatic dynamics simulation. Two representative
model systems, CH<sub>2</sub>NH<sub>2</sub><sup>+</sup> and the phytochromobilin
chromophore model, are chosen to examine the performance of these
dimensionality reduction approaches. The results show that these approaches
are very promising, because they can extract the major molecular motion
from complicated time-dependent molecular evolution without preknown
knowledge
Inclusion of Machine Learning Kernel Ridge Regression Potential Energy Surfaces in On-the-Fly Nonadiabatic Molecular Dynamics Simulation
We
discuss a theoretical approach that employs machine learning
potential energy surfaces (ML-PESs) in the nonadiabatic dynamics simulation
of polyatomic systems by taking 6-aminopyrimidine as a typical example.
The Zhu–Nakamura theory is employed in the surface hopping
dynamics, which does not require the calculation of the nonadiabatic
coupling vectors. The kernel ridge regression is used in the construction
of the adiabatic PESs. In the nonadiabatic dynamics simulation, we
use ML-PESs for most geometries and switch back to the electronic
structure calculations for a few geometries either near the S<sub>1</sub>/S<sub>0</sub> conical intersections or in the out-of-confidence
regions. The dynamics results based on ML-PESs are consistent with
those based on CASSCF PESs. The ML-PESs are further used to achieve
the highly efficient massive dynamics simulations with a large number
of trajectories. This work displays the powerful role of ML methods
in the nonadiabatic dynamics simulation of polyatomic systems
Inclusion of Machine Learning Kernel Ridge Regression Potential Energy Surfaces in On-the-Fly Nonadiabatic Molecular Dynamics Simulation
We
discuss a theoretical approach that employs machine learning
potential energy surfaces (ML-PESs) in the nonadiabatic dynamics simulation
of polyatomic systems by taking 6-aminopyrimidine as a typical example.
The Zhu–Nakamura theory is employed in the surface hopping
dynamics, which does not require the calculation of the nonadiabatic
coupling vectors. The kernel ridge regression is used in the construction
of the adiabatic PESs. In the nonadiabatic dynamics simulation, we
use ML-PESs for most geometries and switch back to the electronic
structure calculations for a few geometries either near the S<sub>1</sub>/S<sub>0</sub> conical intersections or in the out-of-confidence
regions. The dynamics results based on ML-PESs are consistent with
those based on CASSCF PESs. The ML-PESs are further used to achieve
the highly efficient massive dynamics simulations with a large number
of trajectories. This work displays the powerful role of ML methods
in the nonadiabatic dynamics simulation of polyatomic systems
Computational Investigation of Acene-Modified Zinc-Porphyrin Based Sensitizers for Dye-Sensitized Solar Cells
A series
of acene-modified zinc-porphyrin dyes (benzene to pentacene,
denoted as LAC-1 to LAC-5) were chosen to examine their performance
as photosensitizers in dye-sensitized solar cells (DSSCs). Their structural,
electronic, and optical properties were investigated at the DFT/TDDFT
levels using various theoretical models (i.e., the gas phase model
and the implicit/explicit solvent model). The dye@TiO<sub>2</sub> complex
was used to investigate the dye/semiconductor interfaces using both
the cluster and periodic models. After a careful examination of the
dependence of the results on different theoretical approaches, some
basic principles could be derived based on the theoretical investigation
of structure–function relationships in isolated dyes and dye–TiO<sub>2</sub> assemblies. Based on these ideas, some general suggestions
can be proposed for the future design of dyes for use in DSSCs. For
instance, the DFT functionals used in estimating the critical parameters
for DSSCs should be carefully validated. Sometimes the performances
of the DFT functionals can be improved by a specific energy-shift
correction to compensate for systematic errors. Benchmark calculations
indicated that the best approach for depicting the reduction potentials
is either the M06-2X functional combined with the formula Δ<i>E</i><sub>red</sub> = (<i>E</i><sup>0</sup> – <i>E</i><sup>–</sup>)<sub>GS</sub> or the B3LYP functional
combined with Koopman’s Theorem. The best functional for estimating
the excitation energies was found to be LC-ωPBE. The impact
of significant thermal fluctuations on the optoelectronic properties
of dyes may also be an important consideration in the prediction of
more efficient dyes for use DSSCs. In contrast to the selection of
DFT functionals, both the cluster and periodic models resulted in
consistent views of the dye–TiO<sub>2</sub> interactions, indicating
that the use of either model should achieve reasonable results at
least in the qualitative manner
Rigid–Flexible Coupling High Ionic Conductivity Polymer Electrolyte for an Enhanced Performance of LiMn<sub>2</sub>O<sub>4</sub>/Graphite Battery at Elevated Temperature
LiMn<sub>2</sub>O<sub>4</sub>-based
batteries exhibit severe capacity
fading during cycling or storage in LiPF<sub>6</sub>-based liquid
electrolytes, especially at elevated temperatures. Herein, a novel
rigid–flexible gel polymer electrolyte is introduced to enhance
the cyclability of LiMn<sub>2</sub>O<sub>4</sub>/graphite battery
at elevated temperature. The polymer electrolyte consists of a robust
natural cellulose skeletal incorporated with soft segment polyÂ(ethyl
α-cyanoacrylate). The introduction of the cellulose effectively
overcomes the drawback of poor mechanical integrity of the gel polymer
electrolyte. Density functional theory (DFT) calculation demonstrates
that the polyÂ(ethyl α-cyanoacrylate) matrices effectively dissociate
the lithium salt to facilitate ionic transport and thus has a higher
ionic conductivity at room temperature. Ionic conductivity of the
gel polymer electrolyte is 3.3 × 10<sup>–3</sup> S cm<sup>–1</sup> at room temperature. The gel polymer electrolyte
remarkably improves the cycling performance of LiMn<sub>2</sub>O<sub>4</sub>-based batteries, especially at elevated temperatures. The
capacity retention after the 100th cycle is 82% at 55 °C, which
is much higher than that of liquid electrolyte (1 M LiPF<sub>6</sub> in carbonate solvents). The polymer electrolyte can significantly
suppress the dissolution of Mn<sup>2+</sup> from surface of LiMn<sub>2</sub>O<sub>4</sub> because of strong interaction energy of Mn<sup>2+</sup> with PECA, which was investigated by DFT calculation