arXiv subjects

Joseph Eli Subotnik

Publications and source records attributed to Joseph Eli Subotnik.

5 recordsLinked to original sources

arXiv2026

Raman spectroscopy at metal interfaces: A numerical study of the strong coupling regime

We investigate how proximity to a metal nanostructure, particularly to a flat mirror or a cavity confined between two mirrors, affects the vibronic structure of Raman scattering signals. We find that such proximity, particularly for the strong-coupling situation encountered in cavity environments, plays multiple roles in shaping Raman signals beyond the now-familiar signal enhancement known as surface-enhanced Raman scattering (SERS). First, in analogy to the electromagnetic SERS mechanism, near or between mirrors, the local field experienced by a molecule differ from that in vacuum. In particular, between mirrors, the cavity enhances the effective excited state population by trapping the EM field inside it. Second, the nearby metal surface provides a relaxation channel and a lineshape broadening mechanism, and inside a cavity this lineshape is inherited by the cavity polaritons. This relaxation results in a loss of yield but the associated broadening also leads to significant absorption over a larger frequency range. Third, near metallic interfaces interference between incident and reflected light can lead to a richly structured Raman spectrum. For instance, we find that the Rabi contraction (that results from depopulating the ground state) can interfere with Raman signals (and the effect appears to be the same order as Raman itself). These cavity effects are calculated by a full-scale FDTD simulation and highlight the convoluted but fascinating roles of photonic materials on optical signals.

physics.optics↗

arXiv2022

Non-adiabatic Dynamics in a Continuous Circularly Polarized Laser Field with Floquet Phase-space Surface Hopping

Non-adiabatic chemical reactions involving continuous circularly polarized light (cw CPL) have not attracted as much attention as dynamics in unpolarized/linearly polarized light. However, including circularly (in contrast to linearly) polarized light allows one to effectively introduce a complex-valued time-dependent Hamiltonian, which offers a new path for control or exploration through the introduction of Berry forces. Here, we investigate several inexpensive semiclassical approaches for modeling such nonadiabatic dynamics in the presence of a time-dependent complex-valued Hamiltonian, beginning with a straightforward instantaneous adiabatic fewest-switches surface hopping (IA-FSSH) approach (where the electronic states depend on position and time), continuing to a standard Floquet fewest switches surface hopping (F-FSSH) approach (where the electronic states depend on position and frequency), and ending with an exotic Floquet phase-space surface hopping (F-PSSH) approach (where the electronic states depend on position, frequency, and momentum). Using a set of model systems with time-dependent complex-valued Hamiltonians, we show that the Floquet phase-space adiabats are the optimal choice of basis as far as accounting for Berry phase effects and delivering accuracy. Thus, the F-PSSH algorithm sets the stage for modeling nonadiabatic dynamics under strong externally pumped circular polarization in the future.

physics.chem-ph↗

arXiv2019

Non-adiabatic Dynamics in a Laser Field with Floquet Fewest Switches Surface Hopping: The Need for An Accurate Treatment of Coherence and Decoherence Remains

We investigate two well-known approaches for extending the fewest switches surface hopping (FSSH) algorithm to periodic time-dependent couplings. The first formalism acts as if the instantaneous adiabatic electronic states were standard adiabatic states, which just happen to evolve in time. The second formalism replaces the role of the usual adiabatic states by the time-independent adiabatic Floquet states. For a set of modified Tully model problems, the Floquet FSSH (F-FSSH) formalism gives a better estimate for both transmission and reflection probabilities than the instantaneous adiabatic FSSH (IA-FSSH) formalism. More importantly, only F-FSSH predicts the correct final scattering momentum. Finally, in order to use Floquet theory accurately, we find that it is crucial to account for the interference between Floquet states. Our results should be of interest to all those interested in laser induced molecular dynamics.

physics.chem-ph↗

arXiv2019

A Robust and Unified Solution for Choosing the Phases of Adiabatic States as a Function of Geometry: Extending Parallel Transport Concepts to the cases of Trivial & Near Trivial Crossings

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon consideration of the overlap matrix ($\mathbf{U}$) between basis functions at successive points in time and selecting the phases so as to minimize the matrix norm of $\log(\mathbf{U})$. In so doing, one can extend the concept of parallel transport to cases with sharp curve crossings. We demonstrate that this algorithm performs well under extreme situations where dozens of states cross each other either through trivial crossings (where there is zero effective diabatic coupling), or through nontrivial crossings (when there is a nonzero diabatic coupling), or through a combination of both. In all cases, we compute the time-derivative coupling matrix elements (or equivalently non-adiabatic derivative coupling matrix elements) that are as smooth as possible. Our results should be of interest to all who are interested in either non-adiabatic dynamics, or more generally, parallel transport in large systems.

physics.chem-ph↗

arXiv2017

Vibrational Relaxation at a Metal Surface: Electronic Friction Versus Classical Master Equations

Within a 2-D scattering model, we investigate the vibrational relaxation of an idealized molecule colliding with a metal surface. Two perturbative nonadiabatic dynamics schemes are compared: $(i)$ electronic friction (EF) and $(ii)$ classical master equations (CME). In addition, we also study a third approach, $(iii)$ a broadened classical master equation (BCME) that interpolates between approaches $(i)$ and $(ii)$. Two conclusions emerge. First, even though we do not have exact data to compare against, we find there is strong evidence suggesting that EF results may be spurious for scattering problems with more than one nuclear dimension. Second, we find that there is an optimal molecule-metal coupling that maximizes vibrational relaxation rates by inducing large nonadiabatic interactions.

physics.chem-ph↗