University of Oulu

Håkansson, Pär. Prediction of low-field nuclear singlet lifetimes with molecular dynamics and quantum-chemical property surface. Phys. Chem. Chem. Phys., 2017,19, 10237-10254. DOI: 10.1039/C6CP08394C

Prediction of low-field nuclear singlet lifetimes with molecular dynamics and quantum-chemical property surface

Saved in:
Author: Håkansson, Pär1,2
Organizations: 1School of Chemistry, University of Southampton, SO17 1BJ Southampton, UK
2NMR Research Unit, P.O. Box 3000, FIN-90014 University of Oulu, Finland
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 4.5 MB)
Persistent link:
Language: English
Published: Royal Society of Chemistry, 2017
Publish Date: 2018-01-16


Molecular dynamics and quantum chemistry methods are implemented to quantify nuclear spin-1/2 pair singlet-state relaxation rates for three molecular systems at low magnetic field and room temperature. Computational methodology is developed for weak interactions, particularly important for singlet states at low field. These include spin-rotation and spin-internal-motion effects, which describe the coupling of the spin-carrying nuclei to fluctuating local magnetic fields induced by the overall and internal molecular fluctuations, respectively. A high-dimensional tensor property surface using Kriging interpolation is developed to circumvent costly quantum-chemical calculations. Together with the intramolecular dipolar relaxation, all the simulated relaxation mechanisms are accounted for with a common theoretical framework. Comparison with experiment indicates that quantitative accuracy is obtained, sufficient to enable guidance in the molecular design of molecules with long-lived singlet order.

see all

Series: PCCP. Physical chemistry chemical physics
ISSN: 1463-9076
ISSN-E: 1463-9084
ISSN-L: 1463-9076
Volume: 19
Pages: 10237 - 10254
DOI: 10.1039/C6CP08394C
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
Funding: The author acknowledge funding from 291044-HYPERSINGLET grant from the European Research Council and the EU Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant No 703446.
EU Grant Number: (703446) QUNS - Quantum-Statistical Methods for Nuclear Singlet States in Complex Fluids
Copyright information: This journal is © the Owner Societies 2017. Published in this repository with the kind permission of the publisher.