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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Advanced MUltiscaLe materials for key Enabling Technologies</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

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

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Volume of the periodical

26

Issue of the periodical within the volume

39

Country of publishing house

GB - UNITED KINGDOM

Number of pages

6

Pages from-to

25412-25417

UT code for WoS article

001319092500001

EID of the result in the Scopus database

2-s2.0-85205899068