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Main Authors: Armstrong, Jeff, Cavaye, Hamish, Sharma, Pankaj, Potter, Matthew E.
Format: Preprint
Published: 2026
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Online Access:https://arxiv.org/abs/2602.20907
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author Armstrong, Jeff
Cavaye, Hamish
Sharma, Pankaj
Potter, Matthew E.
author_facet Armstrong, Jeff
Cavaye, Hamish
Sharma, Pankaj
Potter, Matthew E.
contents Isotopic substitution modifies nuclear masses without altering the electronic potential energy surface to first order and is therefore often interpreted as a simple rescaling of vibrational frequencies. In solids with dense phonon manifolds, however, mass substitution acts as a parametric Hermitian deformation of the mass-weighted dynamical matrix, generating a continuous family of eigenproblems whose eigenvectors can undergo substantial rotation within coupled subspaces. Here we investigate protiated and deuterated ZIF-8 using inelastic neutron scattering and density functional theory lattice-dynamics calculations. While many vibrational modes exhibit near-ideal mass scaling and preserve their character across isotopic endpoints, modes embedded in spectrally congested regions display pronounced redistribution of vibrational character that cannot be inferred from frequency shifts alone. Because inelastic neutron scattering intensity is directly weighted by hydrogen displacement amplitude, spectral sparsity and congestion provide experimental indicators of predictable frequency renormalisation or susceptibility to qualitative eigenvector reorganisation under deuteration. To establish physically meaningful mode correspondence, we develop an adiabatic eigenvector-continuation framework with overlap-based tracking and explicit stability diagnostics. These results show that vibrational identity in complex framework materials is best understood as a continuous trajectory in eigenvector space and provide a general framework for analysing isotope-induced spectral flow in dense phonon systems.
format Preprint
id arxiv_https___arxiv_org_abs_2602_20907
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Collective Phonon Mixing and Eigenvector Transport Under Isotope Substitution
Armstrong, Jeff
Cavaye, Hamish
Sharma, Pankaj
Potter, Matthew E.
Materials Science
Isotopic substitution modifies nuclear masses without altering the electronic potential energy surface to first order and is therefore often interpreted as a simple rescaling of vibrational frequencies. In solids with dense phonon manifolds, however, mass substitution acts as a parametric Hermitian deformation of the mass-weighted dynamical matrix, generating a continuous family of eigenproblems whose eigenvectors can undergo substantial rotation within coupled subspaces. Here we investigate protiated and deuterated ZIF-8 using inelastic neutron scattering and density functional theory lattice-dynamics calculations. While many vibrational modes exhibit near-ideal mass scaling and preserve their character across isotopic endpoints, modes embedded in spectrally congested regions display pronounced redistribution of vibrational character that cannot be inferred from frequency shifts alone. Because inelastic neutron scattering intensity is directly weighted by hydrogen displacement amplitude, spectral sparsity and congestion provide experimental indicators of predictable frequency renormalisation or susceptibility to qualitative eigenvector reorganisation under deuteration. To establish physically meaningful mode correspondence, we develop an adiabatic eigenvector-continuation framework with overlap-based tracking and explicit stability diagnostics. These results show that vibrational identity in complex framework materials is best understood as a continuous trajectory in eigenvector space and provide a general framework for analysing isotope-induced spectral flow in dense phonon systems.
title Collective Phonon Mixing and Eigenvector Transport Under Isotope Substitution
topic Materials Science
url https://arxiv.org/abs/2602.20907