Exciting DeePMD: Learning excited-state energies, forces, and non-adiabatic couplings.

We extend the DeePMD neural network architecture to predict electronic structure properties necessary to perform non-adiabatic dynamics simulations. While learning the excited state energies and forces follows a straightforward extension of the DeePMD approach for ground-state energies and forces, how to learn the map between the non-adiabatic coupling vectors (NACV) and the local chemical environment descriptors of DeePMD is less trivial. Most implementations of machine-learning-based non-adiabatic dynamics inherently approximate the NACVs, with an underlying assumption that the energy-difference-scaled NACVs are conservative fields. We overcome this approximation, implementing the method recently introduced by Richardson [J. Chem. Phys. 158, 011102 (2023)], which learns the symmetric dyad of the energy-difference-scaled NACV. The efficiency and accuracy of our neural network architecture are demonstrated through the example of the methaniminium cation CH2NH2+.

Reformulation of Time-Dependent Density Functional Theory for Nonperturbative Dynamics: The Rabi Oscillation Problem Resolved.

Rabi oscillations have long been thought to be out of reach in simulations using time-dependent density functional theory (TDDFT), a prominent symptom of the failure of the adiabatic approximation for nonperturbative dynamics. We present a reformulation of TDDFT which requires response quantities only, thus enabling an adiabatic approximation to predict such dynamics accurately because the functional is evaluated on a density close to the ground state, instead of on the fully nonperturbative density. Our reformulation applies to any real-time dynamics, redeeming TDDFT far from equilibrium. Examples of a resonantly-driven local excitation in a model He atom, and charge-transfer in the LiCN molecule are given.

Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states.

Advances in coherent light sources and development of pump-probe techniques in recent decades have opened the way to study electronic motion in its natural time scale. When an ultrashort laser pulse interacts with a molecular target, a coherent superposition of electronic states is created and the triggered electron dynamics is coupled to the nuclear motion. A natural and computationally efficient choice to simulate this correlated dynamics is a trajectory-based method where the quantum-mechanical electronic evolution is coupled to a classical-like nuclear dynamics. These methods must approximate the initial correlated electron-nuclear state by associating an initial electronic wavefunction to each classical trajectory in the ensemble. Different possibilities exist that reproduce the initial populations of the exact molecular wavefunction when represented in a basis. We show that different choices yield different dynamics and explore the effect of this choice in Ehrenfest, surface hopping, and exact-factorization-based coupled-trajectory schemes in a one-dimensional two-electronic-state model system that can be solved numerically exactly. This work aims to clarify the problems that standard trajectory-based techniques might have when a coherent superposition of electronic states is created to initialize the dynamics, to discuss what properties and observables are affected by different choices of electronic initial conditions and to point out the importance of quantum-momentum-induced electronic transitions in coupled-trajectory schemes.

Exact-Factorization-Based Surface Hopping without Velocity Adjustment.

While surface hopping has emerged as a powerful method for simulating non-adiabatic dynamics in large molecules, the ad hoc nature of the necessary velocity adjustments and decoherence corrections in the algorithm somewhat reduces its reliability. Here we propose a new scheme that eliminates these aspects by combining the nuclear equation from the quantum-trajectory surface-hopping approach with the electronic equation derived from the exact-factorization approach. The resulting method, denoted QTSH-XF, yields a surface-hopping method on firmer ground than previous and is shown to successfully capture dynamics in Tully models and in a linear vibronic coupling model of the photoexcited uracil cation.

Oscillator strengths and excited-state couplings for double excitations in time-dependent density functional theory.

Although useful to extract excitation energies of states of double-excitation character in time-dependent density functional theory that are missing in the adiabatic approximation, the frequency-dependent kernel derived earlier [Maitra et al., J. Chem. Phys. 120, 5932 (2004)] was not designed to yield oscillator strengths. These are required to fully determine linear absorption spectra, and they also impact excited-to-excited-state couplings that appear in dynamics simulations and other quadratic response properties. Here, we derive a modified non-adiabatic kernel that yields both accurate excitation energies and oscillator strengths for these states. We demonstrate its performance on a model two-electron system, the Be atom, and on excited-state transition dipoles in the LiH molecule at stretched bond-lengths, in all cases producing significant improvements over the traditional approximations.

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics.

Through approximating electron-nuclear correlation terms in the exact factorization approach, trajectory-based methods have been derived and successfully applied to the dynamics of a variety of light-induced molecular processes, capturing quantum (de)coherence effects rigorously. These terms account for the coupling among the trajectories, recovering the nonlocal nature of quantum nuclear dynamics that is completely overlooked in traditional independent-trajectory algorithms. Nevertheless, some of the approximations introduced in the derivation of some of these methods do not conserve the total energy. We analyze energy conservation in the coupled-trajectory mixed quantum-classical (CTMQC) algorithm and explore the performance of a modified algorithm, CTMQC-E, where some of the terms are redefined to restore energy conservation. A set of molecular models is used as a test, namely, 2-cis-penta-2,4-dienimium cation, bis(methylene) adamantyl radical cation, butatriene cation, uracil radical cation, and neutral pyrazine.

Different flavors of exact-factorization-based mixed quantum-classical methods for multistate dynamics.

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 a given time, and analyze: (1) the use of coupled versus auxiliary trajectories in evaluating the electron-nuclear correlation terms, (2) the approximation of using these terms within surface-hopping and Ehrenfest frameworks, and (3) the relevance of the exact conditions of zero population transfer away from nonadiabatic coupling regions and total energy conservation. Dynamics through the three-state conical intersection in the uracil radical cation as well as polaritonic models in one dimension are studied.

Energy-conserving coupled trajectory mixed quantum-classical dynamics.

The coupled-trajectory mixed quantum-classical method (CTMQC), derived from the exact factorization approach, has successfully predicted photo-chemical dynamics in a number of interesting molecules, capturing population transfer and decoherence from first principles. However, due to the approximations made, CTMQC does not guarantee energy conservation. We propose a modified algorithm, CTMQC-E, which redefines the integrated force in the coupled-trajectory term so to restore energy conservation, and demonstrate its accuracy on scattering in Tully's extended coupling region model and photoisomerization in a retinal chromophore model.

Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory.

The adiabatic approximation in time-dependent density functional theory is known to give an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. We demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Exact Factorization Adventures: A Promising Approach for Non-Bound States.

Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides potentials that act on the nuclear subsystem or electronic subsystem, which contain the effects of the coupling to the other subsystem in an exact way. We briefly review the various applications of the XF idea in different realms, and how features of these potentials aid in the interpretation of two different laser-driven dissociation mechanisms. We present a detailed study of the different ways the coupling terms in recently-developed XF-based mixed quantum-classical approximations are evaluated, where either truly coupled trajectories, or auxiliary trajectories that mimic the coupling are used, and discuss their effect in both a surface-hopping framework as well as the rigorously-derived coupled-trajectory mixed quantum-classical approach.

Exact-Factorization-Based Surface Hopping for Multistate Dynamics.

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF [Ha et al. J. Phys. Chem. Lett. 2018, 9, 1097], introduces an additional term in the electronic equation of surface hopping that couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence, but here we show it is crucial to accurately capture nonadiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multiconfiguration time-dependent Hartree quantum dynamics benchmark.

Analysis of the classical trajectory treatment of photon dynamics for polaritonic phenomena.

Simulating photon dynamics in strong light-matter coupling situations via classical trajectories is proving to be powerful and practical. Here, we analyze the performance of the approach through the lens of the exact factorization approach. Since the exact factorization enables a rigorous definition of the potentials driving the photonic motion, it allows us to identify that the underestimation of photon number and intensities observed in earlier work is primarily due to an inadequate accounting of light-matter correlation in the classical Ehrenfest force rather than errors from treating the photons quasiclassically per se. The latter becomes problematic when the number of photons per mode begins to exceed a half.

Double and Charge-Transfer Excitations in Time-Dependent Density Functional Theory.

Time-dependent density functional theory has emerged as a method of choice for calculations of spectra and response properties in physics, chemistry, and biology, with its system-size scaling enabling computations on systems much larger than otherwise possible. While increasingly complex and interesting systems have been successfully tackled with relatively simple functional approximations, there has also been increasing awareness that these functionals tend to fail for certain classes of approximations. Here I review the fundamental challenges the approximate functionals have in describing double excitations and charge-transfer excitations, which are two of the most common impediments for the theory to be applied in a black-box way. At the same time, I describe the progress made in recent decades in developing functional approximations that give useful predictions for these excitations.

Minimizing the Time-Dependent Density Functional Error in Ehrenfest Dynamics.

Simulating electron-ion dynamics using time-dependent density functional theory within an Ehrenfest dynamics scheme can be done in two ways that are in principle exact and identical: propagating time-dependent electronic Kohn-Sham equations or propagating electronic coefficients on surfaces obtained from linear-response. We show here that using an approximate functional leads to qualitatively different dynamics in the two approaches. We argue that the latter is more accurate because the functionals are evaluated on domains close to the ground state where currently used approximations perform better. We demonstrate this on an exactly solvable model of charge transfer and discuss implications for time-resolved spectroscopy.

Study of the Decoherence Correction Derived from the Exact Factorization Approach for Nonadiabatic Dynamics.

We present a detailed study of the decoherence correction to surface hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and the same electronic structure method are used as a reference for three molecules: ethylene, the methaniminium cation, and fulvene, for which nonadiabatic dynamics follows a photoexcitation. A comparison with the Granucci-Persico energy-based decoherence correction and the augmented fewest-switches surface-hopping scheme shows that the three decoherence-corrected methods operate on individual trajectories in a qualitatively different way, but the results averaged over trajectories are similar for these systems.

Case studies of the time-dependent potential energy surface for dynamics in cavities.

The exact time-dependent potential energy surface driving the nuclear dynamics was recently shown to be a useful tool to understand and interpret the coupling of nuclei, electrons, and photons in cavity settings. Here, we provide a detailed analysis of its structure for exactly solvable systems that model two phenomena: cavity-induced suppression of proton-coupled electron-transfer and its dependence on the initial state, and cavity-induced electronic excitation. We demonstrate the inadequacy of simply using a weighted average of polaritonic surfaces to determine the dynamics. Such a weighted average misses a crucial term that redistributes energy between the nuclear and the polaritonic systems, and this term can in fact become a predominant term in determining the nuclear dynamics when several polaritonic surfaces are involved. Evolving an ensemble of classical trajectories on the exact potential energy surface reproduces the nuclear wavepacket quite accurately, while evolving on the weighted polaritonic surface fails after a short period of time. The implications and prospects for application of mixed quantum-classical methods based on this surface are discussed.

Effect of many modes on self-polarization and photochemical suppression in cavities.

The standard description of cavity-modified molecular reactions typically involves a single (resonant) mode, while in reality, the quantum cavity supports a range of photon modes. Here, we demonstrate that as more photon modes are accounted for, physicochemical phenomena can dramatically change, as illustrated by the cavity-induced suppression of the important and ubiquitous process of proton-coupled electron-transfer. Using a multi-trajectory Ehrenfest treatment for the photon-modes, we find that self-polarization effects become essential, and we introduce the concept of self-polarization-modified Born-Oppenheimer surfaces as a new construct to analyze dynamics. As the number of cavity photon modes increases, the increasing deviation of these surfaces from the cavity-free Born-Oppenheimer surfaces, together with the interplay between photon emission and absorption inside the widening bands of these surfaces, leads to enhanced suppression. The present findings are general and will have implications for the description and control of cavity-driven physical processes of molecules, nanostructures, and solids embedded in cavities.