Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Electron Sextets as Optically Addressable Molecular Qubits: Triplet Carbenes

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5c02672· OSTI ID:2999596
There is a growing demand in quantum information science and sensing for electron spin purification and readout via a spin-optical interface. This technique, known as optically detected magnetic resonance (ODMR), has been applied to diamond-NV centers and transition-metal complexes. Metal-free counterparts of these optically addressable spin qubits promise to be cheaper, more sustainable color centers with prolonged polarization lifetimes. However, progress has been hindered by the low ODMR signals of carbon-based π-diradicals, partly due to the lack of a ground singlet-to-triplet intersystem crossing (ISC). In this work, we propose exploring organic systems that are even more electron-deficient: electron sextets. Using triplet carbenes as an example, we illustrate how the ground singlet-triplet gap can be widened beyond thermal energy with the associated singlet-to-triplet ISC made available by vibronic effects. Through careful molecular engineering, this ISC can occur at a rate similar to and with an opposite spin selectivity from the excited-state ISC well-established in π-diradicals, unlocking a new ODMR pathway with potential signal gains. Persistent triplet carbenes are a renascent field, with multiple stable molecules being isolated in the past five years. To motivate further development of its emissive properties, we illustrate our design in three realistic carbene candidates that incorporate existing strategies for carbene stabilization. Furthermore, we believe that a new realm of quantum materials can be uncovered by expanding our scope toward stable electron sextets.
Research Organization:
California Institute of Technology, Pasadena, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0022089
OSTI ID:
2999596
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 26 Vol. 147; ISSN 0002-7863; ISSN 1520-5126
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (135)

Molecular One‐ and Two‐Qubit Systems with Very Long Coherence Times journal July 2023
Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry journal August 2018
A Highly Stable Organic Luminescent Diradical journal March 2023
A Stable Chichibabin Diradicaloid with Near‐Infrared Emission journal June 2024
Luminescent Mono‐, Di‐, and Triradicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes journal December 2019
Deconvolving Contributions to Decoherence in Molecular Electron Spin Qubits: A Dynamic Ligand Field Approach journal May 2021
Effect of the damping function in dispersion corrected density functional theory journal March 2011
Triplet carbene that is isolated as a solid and bottled for months journal January 2023
TD-DFT benchmarks: A review journal April 2013
The jahn-teller effect journal June 2009
Software update: The ORCA program system—Version 5.0 journal March 2022
Theory predicts triplet ground-state carbene containing the N-heterocyclic carbenic unit journal March 2013
A spin correction procedure for unrestricted Hartree-Fock and Møller-Plesset wavefunctions for singlet diradicals and polyradicals journal September 1988
An overview of the biosensing potential of organometallic compounds journal December 2023
Theoretical designs for triplet ground-state carbenes: A target for experimental studies journal August 2007
Definition of corresponding orbitals and the diradical character in broken symmetry DFT calculations on spin coupled systems journal April 2004
The nitrogen-vacancy colour centre in diamond journal July 2013
Stable organic radical qubits and their applications in quantum information science journal September 2024
The Jahn–Teller Effect book January 2006
From Stable Radicals to Thermally Robust High-Spin Diradicals and Triradicals journal October 2023
Do Diradicals Behave Like Radicals? journal October 2019
Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) as a Simple yet Accurate Method for Diradicals and Diradicaloids journal January 2021
Reliable Diradical Characterization via Precise Singlet–Triplet Gap Calculations: Application to Thiele, Chichibabin, and Müller Analogous Diradicals journal January 2025
Prediction of the Existence of LiCH: A Carbene-like Organometallic Molecule journal November 2020
Multireference Study of Optically Addressable Vanadium-Based Molecular Qubit Candidates journal August 2022
Photoswitching Molecules Functionalized with Optical Cycling Centers Provide a Novel Platform for Studying Chemical Transformations in Ultracold Molecules journal December 2024
Spin–Orbit Coupling Constants in Atoms and Ions of Transition Elements: Comparison of Effective Core Potentials, Model Core Potentials, and All-Electron Methods journal February 2019
Understanding the Energy Gap Law under Vibrational Strong Coupling journal March 2023
Stable Room Temperature Nitrenes Created by Photolysis of Crystalline 4-Azido-2,3,5,6-tetrafluorobenzoic Acid journal February 2023
T1 Anisotropy Elucidates Spin Relaxation Mechanisms in an S = 1 Cr(IV) Optically Addressable Molecular Qubit journal August 2023
Foundations of Quantum Information for Physical Chemistry journal April 2024
Accurate Excitation Energies of Point Defects from Fast Particle–Particle Random Phase Approximation Calculations journal March 2024
Dual Optical Cycling Centers Mounted on an Organic Scaffold: New Insights from Quantum Chemistry Calculations and Symmetry Analysis journal May 2024
Designing Optically Addressable Nitrogen-Vacancy Centers in Ultrasmall Nanodiamonds: Insights from First-Principles Calculations journal February 2025
Spin-State Manipulation in a Luminescent Diradical Polymer journal June 2024
A Telecom O-Band Emitter in Diamond journal March 2023
A Molecular Approach to Quantum Sensing journal April 2021
Optically Distinguishable Electronic Spin-isomers of a Stable Organic Diradical journal April 2024
Enhancing the Optically Detected Magnetic Resonance Signal of Organic Molecular Qubits journal January 2025
Persistent Triplet Carbenes journal August 1997
Diradicals journal July 2013
Persistent Triplet Carbenes journal August 2009
High-spin carbenes journal May 1988
Ground states of molecules. 43. A MINDO/3 study of the rearrangement of phenylcarbene to cycloheptatrienacarbene journal September 1977
Ground states of molecules. XXV. MINDO/3. Improved version of the MINDO semiempirical SCF-MO method journal March 1975
Structure Analysis of a Transient Triplet Carbene Trapped in a Crystal journal June 2001
H−C−SiH3:  Direct Generation and Spectroscopic Identification of Ethylidene's Cousin journal August 2005
Structure Determination of Triplet Diphenylcarbenes by in Situ X-ray Crystallographic Analysis journal January 2007
Carbene Stabilization by Aryl Substituents. Is Bigger Better? journal February 2007
Heterodimetallic [LnLn′] Lanthanide Complexes: Toward a Chemical Design of Two-Qubit Molecular Spin Quantum Gates journal August 2014
Nickel(II) Metal Complexes as Optically Addressable Qubit Candidates journal August 2020
Trigonal Bipyramidal V 3+ Complex as an Optically Addressable Molecular Qubit Candidate journal November 2020
An Open-shell, Luminescent, Two-Dimensional Coordination Polymer with a Honeycomb Lattice and Triangular Organic Radical journal March 2021
Triplet Carbene with Highly Enhanced Thermal Stability in the Nanospace of a Metal–Organic Framework journal May 2021
The Impact of Ligand Field Symmetry on Molecular Qubit Coherence journal October 2021
Three-State Switching of an Anthracene Extended Bis-thiaxanthylidene with a Highly Stable Diradical State journal October 2021
Tunable Cr4+ Molecular Color Centers journal November 2021
Characterization of a Triplet Vinylidene journal December 2021
Could the Quantum Internet Be Comprised of Molecular Spins with Tunable Optical Interfaces? journal November 2022
Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via T1 Anisotropy journal November 2022
Single-Molecule Magnetoluminescence from a Spatially Confined Persistent Diradical Emitter journal June 2023
Thiele’s Fluorocarbons: Stable Diradicaloids with Efficient Visible-to-Near-Infrared Fluorescence from a Zwitterionic Excited State journal July 2023
Oriented Triplet Excitons as Long-Lived Electron Spin Qutrits in a Molecular Donor–Acceptor Single Cocrystal journal December 2023
Sulfone-Functionalized Chichibabin’s Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm journal February 2024
Spin-Correlated Luminescence of a Carbazole-Containing Diradical Emitter: Single-Molecule Magnetoluminescence and Thermally Activated Emission journal June 2024
Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits journal May 2024
A Lead(II) Substituted Triplet Carbene journal October 2024
Room-Temperature Optical Spin Polarization of an Electron Spin Qudit in a Vanadyl-Free Base Porphyrin Dimer journal December 2024
Luminescent Organic Triplet Diradicals as Optically Addressable Molecular Qubits journal September 2024
Molecular Engineering of Emissive Molecular Qubits Based on Spin-Correlated Radical Pairs journal March 2025
The Second Quantum Revolution: Role and Challenges of Molecular Chemistry journal June 2019
Theoretical Exploration of Energy Transfer and Single Electron Transfer Mechanisms to Understand the Generation of Triplet Nitrene and the C(sp3)–H Amidation with Photocatalysts journal November 2022
DFT Studies of Biarylcarbenes and the Carbene−Biradical Continuum journal November 2003
Electronic Stabilization of Ground State Triplet Carbenes journal November 2007
Post-Hartree−Fock Studies on the Structure of Bis(ortho-substituted phenyl)methylenes journal January 2005
Singlet–Triplet Energy Gaps for Diradicals from Particle–Particle Random Phase Approximation journal April 2015
Free Radical Terminology journal November 1938
Generation and characterization of a fairly stable triplet carbene journal August 2001
High-sensitivity diamond magnetometer with nanoscale resolution journal September 2008
A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties journal November 2023
Triplet-mediated spin entanglement between organic radicals: integrating first principles and open-quantum-system simulations journal December 2023
Entangled spin-polarized excitons from singlet fission in a rigid dimer journal March 2023
Mesitylated trityl radicals, a platform for doublet emission: symmetry breaking, charge-transfer states and conjugated polymers journal July 2023
Modulation of triplet quantum coherence by guest-induced structural changes in a flexible metal-organic framework journal September 2024
Molecular spins for quantum computation journal March 2019
Tetrafluorenofulvalene as a sterically frustrated open-shell alkene journal October 2023
Triplet carbenes with transition-metal substituents journal August 2024
Isolation and characterization of a triplet nitrene journal November 2024
Initialization and read-out of intrinsic spin defects in a van der Waals crystal at room temperature journal February 2020
Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes journal June 2020
Single-spin resonance in a van der Waals embedded paramagnetic defect journal May 2021
Quantum technologies with optically interfaced solid-state spins journal August 2018
Exploiting chemistry and molecular systems for quantum information science journal July 2020
Atomic-scale imaging of a 27-nuclear-spin cluster using a quantum sensor journal December 2019
Reversible spin-optical interface in luminescent organic radicals journal August 2023
Decoupling excitons from high-frequency vibrations in organic molecules journal May 2024
Singlet fission for quantum information and quantum computing: the parallel JDE model journal October 2020
Design of an open-shell nitrogen-centered diradicaloid with tunable stimuli-responsive electronic properties journal October 2022
Measuring molecular magnets for quantum technologies journal July 2021
Molecular spin qudits for quantum algorithms journal January 2018
A stable triplet diradical emitter journal January 2021
Chemical control of spin–lattice relaxation to discover a room temperature molecular qubit journal January 2022
Electro-optical π-radicals: design advances, applications and future perspectives journal January 2022
Electron interaction in unsaturated hydrocarbons journal January 1953
Derivation and Analysis of the Pariser–Parr–Pople Model journal July 1968
A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. II journal May 1953
Spin—Orbit Coupling and the Radiationless Processes in Nitrogen Heterocyclics journal June 1963
First-principles calculations of zero-field splitting parameters journal July 2006
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Theory of π-electron states in polydiacetylene molecules journal January 1988
MC-PDFT can calculate singlet–triplet splittings of organic diradicals journal February 2018
Nature of ground and electronic excited states of higher acenes journal August 2016
Concerning Jahn-Teller Effects journal June 1975
The energy gap law for radiationless transitions in large molecules journal February 1970
Electronic Structure of Ions of m-Phenylenebis(phenylmethylene)
  • Ikawa, Atsushi; Mizouchi, Hideo; Fukutome, Hideo
  • Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 271, Issue 1 https://doi.org/10.1080/10587259508034048
journal September 1995
Magnetic-field-dependent photodynamics of single NV defects in diamond: an application to qualitative all-optical magnetic imaging journal October 2012
A molecular perspective on quantum information journal November 2023
Excited-state dynamics and optically detected magnetic resonance of solid-state spin defects from first principles journal November 2024
Spin-dependent recombination and electroluminescence quantum yield in conjugated polymers journal January 2001
Spin-orbit interactions between interchain excitations in conjugated polymers journal January 2010
Avoiding power broadening in optically detected magnetic resonance of single NV defects for enhanced dc magnetic field sensitivity journal November 2011
Spin-orbit coupling and its effects in organic solids journal March 2012
Room-Temperature Optically Detected Coherent Control of Molecular Spins journal September 2024
Quantum sensing of magnetic fields with molecular color centers journal November 2023
Room-temperature quantum sensing with photoexcited triplet electrons in organic crystals journal February 2025
Enhancing Spin Coherence in Optically Addressable Molecular Qubits through Host-Matrix Control journal August 2022
Quantum sensing journal July 2017
On the electronic structure of alternant conjugated organic radicals for light-emitting diode applications conference August 2021
Near-infrared luminescent open-shell π-conjugated systems with a bright lowest-energy zwitterionic singlet excited state journal July 2024
Unconditional quantum teleportation between distant solid-state quantum bits journal May 2014
Observation of an environmentally insensitive solid-state spin defect in diamond journal July 2018
Optically addressable molecular spins for quantum information processing journal November 2020
A stable rhodium-coordinated carbene with a σ 0 π 2 electronic configuration journal January 2024
Synthesis of a stable crystalline nitrene journal July 2024
Ultrafast all-optical coherence of molecular electron spins in room-temperature water solution journal November 2024

Similar Records

Enhancing the Optically Detected Magnetic Resonance Signal of Organic Molecular Qubits
Journal Article · Wed Jan 01 23:00:00 EST 2025 · ACS Central Science · OSTI ID:2999597

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits
Journal Article · Mon May 27 00:00:00 EDT 2024 · Journal of the American Chemical Society · OSTI ID:2999598

C{sub 3}H{sub 4}: Theoretical study of structures and stabilities of isomers
Journal Article · Wed May 15 00:00:00 EDT 1996 · International Journal of Quantum Chemistry · OSTI ID:433464