Experimental Quantification of Spin-Phonon Coupling in Molecular Qubits using Inelastic Neutron Scattering

TL;DR

This study introduces an experimental method combining vibrational spectra and spin relaxation rates to quantify spin-phonon coupling in molecular qubits, revealing how molecular structure influences coherence at different temperatures.

Contribution

It provides a new experimental framework to measure spin-phonon coupling contributions from different vibrational spectral regions in molecular spin systems.

Findings

Weakly coupled lattice modes dominate below 40 K.

Optical phonons above 185 cm^{-1} drive relaxation above 40 K.

Structural modifications can reduce spin-phonon coupling and enhance room-temperature coherence.

Abstract

Electronic spin superposition states enable nanoscale sensing through their sensitivity to the local environment, yet their sensitivity to vibrational motion also limits their coherence times. In molecular spin systems, chemical tunability and atomic-scale resolution are accompanied by a dense, thermally accessible phonon spectrum that introduces efficient spin relaxation pathways. Despite extensive theoretical work, there is little experimental consensus on which vibrational energies dominate spin relaxation or how molecular structure controls spin-phonon coupling (SPC). We present a fully experimental method to quantify SPC coefficients by combining temperature-dependent vibrational spectra from inelastic neutron scattering with spin relaxation rates measured by electron paramagnetic resonance. We apply this framework to two model S = 1/2 systems, copper(II) phthalocyanine (CuPc) and copper(II) octaethylporphyrin (CuOEP). Two distinct relaxation regimes emerge: below 40 K, weakly coupled lattice modes below $50~\mathrm{cm}^{-1}$ dominate, whereas above 40 K, optical phonons above ~$185~\mathrm{cm}^{-1}$ become thermally populated and drive relaxation with SPC coefficients nearly three orders of magnitude larger. Structural distortions in CuOEP that break planar symmetry soften the crystal lattice and enhance anharmonic scattering, but also raise the energy of stretching modes at the molecular core where the spins reside. This redistributes vibrational energy toward the molecular periphery and out of plane, ultimately reducing SPC relative to CuPc and enabling room-temperature spin coherence in CuOEP. Although our method does not provide mode-specific SPC coefficients, it quantifies contributions from distinct spectral regions and establishes a broadly applicable, fully experimental link between crystal structure, lattice dynamics, and spin relaxation.