On the accuracy of the state space restriction approximation for spin dynamics simulations

TL;DR

This paper develops an algebraic framework for the state space restriction approximation in spin dynamics simulations, providing criteria and minimal basis sets for accurate results across various spectroscopic methods.

Contribution

It introduces a rigorous algebraic foundation and applicability criteria for the state space restriction method in spin dynamics, with minimal basis set requirements.

Findings

State space restriction yields accurate results when relaxation and experiment time scales match.

Rigorous error bounds for the approximation are derived.

Applicability demonstrated across NMR, ESR, DNP, and Spin Chemistry simulations.

Abstract

We present an algebraic foundation for the state space restriction approximation in spin dynamics simulations and derive applicability criteria as well as minimal basis set requirements for practically encountered simulation tasks. The results are illustrated with NMR, ESR, DNP and Spin Chemistry simulations. It is demonstrated that state space restriction yields accurate results in systems where the time scale of spin relaxation processes approximately matches the time scale of the experiment. Rigorous error bounds and basis set requirements are derived.