Heteroatom-vacancy centres in molecular nanodiamonds: a computational study of organic molecules possessing triplet ground states through σ-overlap

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00599057" target="_blank" >RIV/61388955:_____/24:00599057 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp02667e" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp02667e</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4cp02667e" target="_blank" >10.1039/d4cp02667e</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Heteroatom-vacancy centres in molecular nanodiamonds: a computational study of organic molecules possessing triplet ground states through σ-overlap

Popis výsledku v původním jazyce

Small molecules possessing a triplet ground state are fundamentally intriguing but also in high demand for applications such as quantum sensing and quantum computing. Such molecules are rare, and most examples involve extended pi-systems. Topology and shape of the spin density will be very different for molecules where the triplet state arises from sigma-overlap. Drawing inspiration from NV- (anionic nitrogen-vacancy) centres in a diamond crystal, which possess triplet ground states that are robust due to the distortion-preventing crystal lattice, we investigate hetero-atom substituted diamondoids (molecular nanodiamonds) as molecular mimics for NV- centres. It is found that even in these small systems, distortions that stabilize singlet states are energetically costly, and the triplet states are more stable than the singlets. The stabilization of the triplet over the singlet is 13, 16, and 18 kcal mol-1, in anionic C3v-C33H36N- and in the charge-neutral molecules C3v-C33H36O and C3v-C33H36S, respectively, using CAM-B3LYP-D3(BJ)/Def2-QZVPP. Comparable numbers are obtained with other density functional theory (DFT) methods, including double-hybrids. Wavefunction-based approaches on the other hand disagree in their predictions: While the MP2 method applied with the DLPNO approximation predicts a preference for the singlet, density matrix renormalization group (DMRG) calculations qualitatively agree with DFT in their prediction of a triplet ground state, although by a small margin, for C3v-C33H36N- and C3v-C33H36O, but not for C3v-C33H36S. Weighing the evidence, we conclude, with reasonable confidence for C3v-C33H36N- and C3v-C33H36O and lesser confidence for C3v-C33H36S, that the ground state for the molecular nanodiamonds studied is a triplet state.

Název v anglickém jazyce

Heteroatom-vacancy centres in molecular nanodiamonds: a computational study of organic molecules possessing triplet ground states through σ-overlap

Popis výsledku anglicky

Small molecules possessing a triplet ground state are fundamentally intriguing but also in high demand for applications such as quantum sensing and quantum computing. Such molecules are rare, and most examples involve extended pi-systems. Topology and shape of the spin density will be very different for molecules where the triplet state arises from sigma-overlap. Drawing inspiration from NV- (anionic nitrogen-vacancy) centres in a diamond crystal, which possess triplet ground states that are robust due to the distortion-preventing crystal lattice, we investigate hetero-atom substituted diamondoids (molecular nanodiamonds) as molecular mimics for NV- centres. It is found that even in these small systems, distortions that stabilize singlet states are energetically costly, and the triplet states are more stable than the singlets. The stabilization of the triplet over the singlet is 13, 16, and 18 kcal mol-1, in anionic C3v-C33H36N- and in the charge-neutral molecules C3v-C33H36O and C3v-C33H36S, respectively, using CAM-B3LYP-D3(BJ)/Def2-QZVPP. Comparable numbers are obtained with other density functional theory (DFT) methods, including double-hybrids. Wavefunction-based approaches on the other hand disagree in their predictions: While the MP2 method applied with the DLPNO approximation predicts a preference for the singlet, density matrix renormalization group (DMRG) calculations qualitatively agree with DFT in their prediction of a triplet ground state, although by a small margin, for C3v-C33H36N- and C3v-C33H36O, but not for C3v-C33H36S. Weighing the evidence, we conclude, with reasonable confidence for C3v-C33H36N- and C3v-C33H36O and lesser confidence for C3v-C33H36S, that the ground state for the molecular nanodiamonds studied is a triplet state.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Pokročilé víceškálové materiály pro nosné klíčové technologie</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

26

Číslo periodika v rámci svazku

39

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

25412-25417

Kód UT WoS článku

001319092500001

EID výsledku v databázi Scopus

2-s2.0-85205899068