A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N’,N’-Tetrasubstituted p-Phenylenediamine Radical Cations
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A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N’,N’-Tetrasubstituted p-Phenylenediamine Radical Cations. / Gleeson, Ronan; Andersen, Cecilie Lindholm; Rapta, Peter; Machata, Peter; Christensen, Jørn Bolstad; Hammerich, Ole; Sauer, Stephan P. A.
I: International Journal of Molecular Sciences (Online), Bind 24, Nr. 4, 3447, 08.02.2023.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N’,N’-Tetrasubstituted p-Phenylenediamine Radical Cations
AU - Gleeson, Ronan
AU - Andersen, Cecilie Lindholm
AU - Rapta, Peter
AU - Machata, Peter
AU - Christensen, Jørn Bolstad
AU - Hammerich, Ole
AU - Sauer, Stephan P. A.
PY - 2023/2/8
Y1 - 2023/2/8
N2 - A test set of N,N,N’,N’-tetrasubstituted p-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised “J-style” basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, ωB97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an R2 value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded.
AB - A test set of N,N,N’,N’-tetrasubstituted p-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised “J-style” basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, ωB97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an R2 value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded.
U2 - 10.3390/ijms24043447
DO - 10.3390/ijms24043447
M3 - Journal article
C2 - 36834859
VL - 24
JO - International Journal of Molecular Sciences (Online)
JF - International Journal of Molecular Sciences (Online)
SN - 1661-6596
IS - 4
M1 - 3447
ER -
ID: 335342778