Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics.

We present a general linear-response method for including nonequilibrium solvation effects (solvent friction effects) in variational transition state theory with multidimensional tunneling (VTST/MT) for calculating reaction rate constants in solution. The generalized Langevin approach is used to include a collective solvent coordinate into VTST/MT, and a general prescription is suggested for coupling this collective solvent coordinate to the solute, which is treated in its full dimensionality. The new formalism is illustrated by application to the aqueous free radical reaction H + CH3OH → H2 + CH2OH at 298 K. This reaction is treated with a linear mixing of Hartree−Fock theory and Austin Model 1 with specific reaction parameters (HF||AM1-SRP). The results with nonequilibrium solvation (NES) are compared to those obtained earlier with the separable equilibrium solvation (SES) and the equilibrium solvation path (ESP) approximations. We focus on the speedup due to solvation and on the kinetic isotope effects...

Nonequilibrium Solvation Effects for a Polyatomic Reaction in Solution

The Fokker–Planck–Kramers equation for a system composed by a reactive coordinate x coupled to a solvent coordinate y is employed to study the effect of additional degrees of freedom on the dynamics of reactive events. The system is studied numerically in the diffusional regimes of both coordinates, for different topologies of the bistable potential function and anisotropies of friction. The eigenvalue spectrum is evaluated by representing the time evolution operator over a basis set of orthonormal functions. A detailed analysis of the effect of the explicit consideration of the slow nonreactive mode is carried on to show that a variation of qualitative picture (scenario) of the reaction dynamics occurs when friction along different directions is strongly anisotropic, depending also on the structure of the two‐dimensional potential surface. The numerical study supports both the qualitative picture of the reaction dynamics and the rate constant expressions obtained analytically. For those cases where the Langer theory has a restricted range of applicability because of the change in the reaction dynamics scenario, this fact has been numerically demonstrated. Here the Langer expression for the rate constant is replaced by the one obtained as a result of the consideration of the effective one‐dimensional problem along the solvent coordinate, characterized by a smaller activation energy than that in the initial problem. All of these facts were confirmed by the numerical test, which shows a satisfactory agreement with the analytical results.

Numerical test of Kramers reaction rate theory in two dimensions

Reaction dynamics for heavy particle charge transfer reactions in polar solvents and ion dielectric friction

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of <strong>{limit}</strong> columns in the table. Remove at least <strong>1</strong> column to add or create another one.

S.A. Dudko

Author Tools

Chat about Author

Papers

Reaction dynamics for heavy particle charge transfer reactions in polar solvents and ion dielectric friction