Related papers: State Space Path Integrals for Electronically Nona…
In Part I [J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory by taking the t->0+ (short-time) limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This…
We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method…
Proton-coupled electron transfers (PCET) are elementary steps in electrocatalysis. However, accurate calculations of PCET rates remain challenging, especially considering nuclear quantum effects (NQEs) under a constant potential condition.…
Constructing an accurate approximation to nonadiabatic rate theory which is valid for arbitrary values of the electronic coupling has been a long-standing challenge in theoretical chemistry. Ring-polymer instanton theories offer a very…
A scarcity of known chemical kinetic parameters leads to the use of many reaction rate estimates, which are not always sufficiently accurate, in the construction of detailed kinetic models. To reduce the reliance on these estimates and…
Recently, the technique of counterdiabatic driving, which provides an effective strategy for accelerating adiabatic quantum evolution, has been widely applied in the preparation of many-body quantum states. In this work, we propose a…
Exceptional points (EPs) have attracted extensive research interest due to their intriguing properties. One of the hallmarks of EP physics is that dynamically encircling the EPs induces chiral mode switching, arising from the breakdown of…
Marcus theory is fundamental to describing electron transfer reactions and quantifying their rates, effectively representing the energy surface associated with an electron transfer from the reactant to the product ionic state via parabolas…
We present a new method for the numerical calculation of canonical reaction rate constants in complex molecular systems, which is based on a path integral formulation of the flux-flux correlation function. Central is the partitioning of the…
On the basis of the method of iterative summation of path integrals (ISPI), we develop a numerically exact transfer-matrix method to describe the nonequilibrium properties of interacting quantum-dot systems. For this, we map the ISPI scheme…
Electrochemical kinetics at electrode-electrolyte interfaces limit performance of devices including fuel cells and batteries. While the importance of moving beyond Butler-Volmer kinetics and incorporating the effect of electronic density of…
Transition State Theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when…
The Wolynes theory of electronically nonadiabatic reaction rates [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is based on a saddle point approximation to the time integral of a reactive flux autocorrelation function in the nonadiabatic…
Conceptualization, theory, method developments and implementations are always of great importance and an interesting task to explore a new dimension in science and technology, which is highly solicited for various functional-driven…
In this letter we propose a model which explains ultrafast and efficient photoisomerization reactions as driven by transitions between quasistationary states of one dimensional (1D) double well potential of an excited electronic state. This…
Electron transfer (ET) across molecular chains including an impurity is studied based on a recently improved real-time path integral Monte Carlo (PIMC) approach [J. Chem. Phys. {\bf 121}, 12696 (2004)]. The reduced electronic dynamics is…
Variational calculations of excited electronic states are carried out by finding saddle points on the surface that describes how the energy of the system varies as a function of the electronic degrees of freedom. This approach has several…
A path integral approach has been generalized for the non-relativistic electron charge transfer processes. The charge transfer - the capture of an electron by an ion passing another atom or more generally the problem of rearrangement…
We derive an exact, continuous-variable path integral (PI) representation of the canonical partition function for electronically nonadiabatic systems. Utilizing the Stock-Thoss (ST) mapping for an N-level system, matrix elements of the…
Spin-exchange collisions have been widely studied in recent years, and various quantum-mechanical scattering approaches have been developed to calculate the rates. However, these methods based on global knowledge of wavefunctions can be…