Macroscopic sample shape effect on pulse electron double resonance (PELDOR) signal

Abstract

Pulse electron double resonance (PELDOR), also called double electron–electron resonance (DEER), is a technique capable of measuring the strength of electron spin dipolar interactions, revealing spin–spin distance distributions in ordered and disordered solid materials. Previous work has shown that PELDOR signals acquire an out-of-phase component under conditions of high electron spin polarization, such as at low temperatures and high fields. In this paper, we show theoretically and experimentally that the size and sign of this effect depends on the macroscopic shape of the sample and its orientation in the external magnetic field. This effect is caused by dipolar interactions between distant spins and provides new insights into the fundamental physics of PELDOR.