Machine Learned Potential Enables Molecular Dynamics Simulation to Predict the Experimental Branching Ratios in the NO Release Channel of Nitroaromatic Compounds.

This study employs a machine learning (ML) model using the Gaussian process regression algorithm to generate potential energy surfaces (PES) from density functional theory calculations, facilitating the investigation of photodissociation dynamics of nitroaromatic compounds, resulting in NO release. The experimentally observed trends in the slow-to-fast branching ratios of the NO moiety were captured by estimating the branching ratio between the two distinct reaction pathways, viz., roaming and oxaziridine mechanisms, calculated from molecular dynamics simulations performed on a reduced two-dimensional T surface.

Exciton energy transfer inside cavity-A benchmark study of polaritonic dynamics using the surface hopping method.

Strong coupling between the molecular system and photon inside the cavity generates polaritons, which can alter reaction rates by orders of magnitude. In this work, we benchmark the surface hopping method to simulate non-adiabatic dynamics in a cavity. The comparison is made against a numerically exact method (the hierarchical equations of motion) for a model system investigating excitonic energy transfer for a broad range of parameters.

Electronic energy transfer in molecular wire: Coherences in the presence of anharmonicity.

Electronic energy transfer in molecular wires is usually theoretically investigated with a harmonic bath to model the environment. The present study is a continuation of our previous work [A. Sindhu and A.

Can classical mechanics sense conical intersection?

Conical intersection (CI) leads to fast electronic energy transfer. However, Hamm and Stock [Phys. Rev.

Metal-Induced Fast Vibrational Energy Relaxation: Quantum Nuclear Effects Captured in Diabatic Independent Electron Surface Hopping (IESH-D) Method.

In this paper, we propose a simple approach to include quantum nuclear effects in the weak electronic coupling regime within the independent electron surface hopping (IESH) method for simulating nonadiabatic dynamics near metal surfaces. Our method uses electronic states in a diabatic basis, and electronic transitions between metal and molecular states are included using Landau-Zener theory. We benchmark our novel approach using a two-state model system for which exact results (obtained from Fermi's golden rule) are available.

An efficient decoherence scheme for fewest switches surface hopping method.

The fewest switches surface hopping method, in its original form, is known to be over-coherent. An accurate and efficient decoherence scheme is still a question of concern in the community. We propose a modification of the augmented fewest switches surface hopping (A-FSSH) scheme to make it efficient without compromising on its accuracy.

Pedagogical Overview of the Fewest Switches Surface Hopping Method.

The fewest switches surface hopping method continues to grow in popularity to capture electronic nonadiabaticity and quantum nuclear effects due to its simplicity and accuracy. Knowing the basics of the method is essential for the correct implementation and interpretation of results. This review covers the fundamentals of the fewest switches surface hopping method with a detailed discussion of the nuances such as decoherence schemes and frustrated hops and the correct approach to calculating populations.

High sensitivity label-free detection of HER2 using an Al-GaN/GaN high electron mobility transistor-based biosensor.

This work reports rapid, label-free and specific detection of the HER2 antigen using a gallium nitride (GaN) high electron mobility transistor (HEMT). Thiol-based chemistry has been utilized to immobilize the corresponding HER2 antibody in the sensing area of the sensor. The formation of a gold-sulfur complex has been confirmed through Raman spectroscopy, giving a peak at around a wavelength of 260 cm.

Coherence and Efficient Energy Transfer in Molecular Wires: Insights from Surface Hopping Simulations.

Understanding the dynamics of electronic energy transfer through a molecular wire is essential to understand the working of natural processes like photosynthesis. We investigate simpler 2 and 3-site model Hamiltonians in this work to understand the importance of coherence to efficient energy transfer. We compare the results of surface hopping simulation with that of numerically exact results and rate theories.

Benchmarking the Surface Hopping Method to Include Nuclear Quantum Effects.

We have benchmarked the surface hopping method to capture nuclear quantum effects in the spin-Boson model in the deep tunneling regime. The thermal populations and the rate constants calculated using the surface hopping method are compared with those calculated using Boltzmann theory and Fermi's golden rule, respectively. Additionally, we have proposed a simple kinetic model that partially includes nuclear quantum effects within Marcus theory, and the results of the surface hopping method are analyzed under the framework of this simple kinetic model.

Simple and Efficient Theoretical Approach To Compute 2D Optical Spectra.

A highly efficient scheme is proposed and benchmarked to compute 2D optical spectra. This scheme is ideally designed for electronic spectroscopy; however, the method can be applied in a straightforward way to vibrational spectroscopy as well. Our scheme performs dynamics only for the t duration, eliminating explicit t and t coherent dynamics and thus can achieve dramatic improvements in efficiency.

Vibrational Energy Relaxation: A Benchmark for Mixed Quantum-Classical Methods.

We investigate the ability of mixed quantum-classical methods to capture the dynamics of vibrational energy relaxation. Several methods, including surface hopping, and Ehrenfest and symmetrical quasiclassical (SQC) dynamics, are benchmarked for the exactly solvable model problem of a harmonic oscillator bilinearly coupled to a bath of harmonic oscillators. Results show that, very often, one can recover accurate vibrational relaxation rates and detailed balance using simple mixed quantum-classical approaches.

Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework.

We employ surface hopping trajectories to model the short-time dynamics of gas-phase and partially solvated 4-(N,N-dimethylamino)benzonitrile (DMABN), a dual fluorescent molecule that is known to undergo a nonadiabatic transition through a conical intersection. To compare theory vs time-resolved fluorescence measurements, we calculate the mixed quantum-classical density matrix and the ensemble averaged transition dipole moment. We introduce a diabatization scheme based on the oscillator strength to convert the TDDFT adiabatic states into diabatic states of L and L character.

An Efficient, Augmented Surface Hopping Algorithm That Includes Decoherence for Use in Large-Scale Simulations.

We propose and implement a highly efficient augmented surface hopping algorithm that (i) can be used for large simulations (with many nuclei and many electronic states) and (ii) includes the effects of decoherence without parametrization. Our protocol is based on three key modifications of the surface hopping methodology: (a) a novel separation of classical and quantum degrees of freedom that treats avoided and trivial crossings efficiently, (b) a multidimensional approximation of the time derivative matrix that avoids explicit construction of the derivative coupling at most time steps, and (c) an efficient approximation for the augmented fewest-switches surface hopping decoherence rate. We will show that this protocol can be several orders of magnitude more efficient than the traditional protocol for large multidimensional problems.

Dynamics of Barrier Crossings for the Generalized Anderson-Holstein Model: Beyond Electronic Friction and Conventional Surface Hopping.

We investigate barrier crossings within the context of the Anderson-Holstein model, as relevant to coupled nuclear-electronic dynamics near a metal surface. Beyond standard electronic friction or conventional surface-hopping dynamics, we show that a broadened classical master equation can recover both the correct nonadiabatic and the correct adiabatic dynamics for a general escape problem (even with possibly multiple escape channels). In the case of a large barrier with only a single escape channel, we also find a surprising conclusion: electronic friction can recover Marcus's nonadiabatic theory of electron transfer in the limit of small molecule-metal couplings.

An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability.

We study several recent mean-field semiclassical dynamics methods, focusing on the ability to recover detailed balance for long time (equilibrium) populations. We focus especially on Miller and Cotton's [J. Phys.

Understanding the Surface Hopping View of Electronic Transitions and Decoherence.

We present a current, up-to-date review of the surface hopping methodology for solving nonadiabatic problems, 25 years after Tully published the fewest switches surface hopping algorithm. After reviewing the original motivation for and failures of the algorithm, we give a detailed examination of modern advances, focusing on both theoretical and practical issues. We highlight how one can partially derive surface hopping from the Schrödinger equation in the adiabatic basis, how one can change basis within the surface hopping algorithm, and how one should understand and apply the notions of decoherence and wavepacket bifurcation.

Does Nonadiabatic Transition State Theory Make Sense Without Decoherence?

We analyze thermal rate constants as computed with surface hopping dynamics and resolve certain inconsistencies that have permeated the literature. On one hand, according to Landry and Subotnik (J. Chem.

Surface hopping, transition state theory, and decoherence. II. Thermal rate constants and detailed balance.

We investigate a simple approach to compute a non-adiabatic thermal rate constant using the fewest switches surface hopping (FSSH) dynamics. We study the effects of both decoherence (using our augmented-FSSH (A-FSSH) algorithm) and forbidden hops over a large range of parameters, including high and low friction regimes, and weak and strong electronic coupling regimes. Furthermore, when possible, we benchmark our results against exact hierarchy equations of motion results, where we usually find a maximum error of roughly a factor of two (at reasonably large temperatures).

Surface hopping, transition state theory and decoherence. I. Scattering theory and time-reversibility.

We provide an in-depth investigation of transmission coefficients as computed using the augmented-fewest switches surface hopping algorithm in the low energy regime. Empirically, microscopic reversibility is shown to hold approximately. Furthermore, we show that, in some circumstances, including decoherence on top of surface hopping calculations can help recover (as opposed to destroy) oscillations in the transmission coefficient as a function of energy; these oscillations can be studied analytically with semiclassical scattering theory.

Tunneling splittings in formic acid dimer: an adiabatic approximation to the Herring formula.

Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch.

Vibrational relaxation of chloroiodomethane in cold argon.

Electronically exciting the C-I stretch in the molecule chloroiodomethane CH2ClI embedded in a matrix of argon at 12 K can lead to an isomer, iso-chloroiodomethane CH2Cl-I, that features a chlorine iodine bond. By temporally probing the isomer at two different frequencies of 435 nm and 485 nm, multiple timescales for isomerization and vibrational energy relaxation were inferred [T. J.