Quantum Processes in Macromolecular Systems
π-conjugated molecules (e.g., polymers, nanotubes, porphyrins and DNA) occur widely in many biological and synthetic systems; for example, in polymer optoelectronic devices and light harvesting complexes.
These systems are characterised by both strong electron-electron interactions and electron-nuclear coupling, and are subject to spatial and temporal disorder. Part of my research is focussed on understanding the effect of these interactions on the electronic and optical properties of conjugated macromolecules. Another goal is to understand excited state dynamics, from ultrafast decoherence and localization processes to post-ps exciton migration and diffusion, and to relate these predictions to experimental observables.
Further aims are to predict how the electronic and optical behaviour of condensed phase systems are determined by the multiscale structures of the component molecules, as well as the inverse problem: how experimental observables coupled with theoretical modelling can help determine multiscale structures.
These goals are being pursued using a variety of theoretical methods and computational techniques (e.g., DMRG (including time-dependent DMRG), MPS methods, and CI-S) on a wide variety of models (e.g., Pariser-Parr-Pople, Hubbard-Peierls, and Frenkel-Holstein models).
Recent work is listed below under "Selected Publications".
I am a member of the Oxford Theoretical Chemistry Group and the Centre for Doctoral Training in Theory and Modelling in Chemical Sciences (TMCS).
Students interested in Part II projects are welcome to contact me about potential projects. Prospective DPhil/PhD students should apply here or to the CDT in TMCS.
My current projects include:
Singlet fission in carotenoids. Singlet fission in polyacenes and carotenoids has the potential to enhance the efficiency of photovoltaic devices. It is also a fascinating process in its own right, because it requires an understanding of the roles of electronic correlation, electron-phonon coupling, and the coupling of a quantum system to its environment. My group, in collaboration with experimentalists at the University of Sheffield, is applying the t-DMRG and TEBD methods to model Hamiltonians in order to understand this mechanism in polyenes (especially carotenoids).
There are two complementary strands to this work. First, we are investigating state interconversion from the optically excited singlet state (S2) to triplet-pair states (see Phys Rev B 102, 125107 (2020)). Second, we are investigating the decoherence and disentanglement of triplet-pair states to become spin-uncorrelated (non-geminate) triplet pairs (see Phys Rev B 102, 035134 (2020)).
Modelling exciton and charge dynamics in conformationally disordered polymers in a dissipative environment. The images shown below are surface plots of exciton wavefunctions, Φ, in the light emitting polymer poly(para-phenylene) (shown above). r is the electron-hole separation and R is the electron-hole centre-of-mass position (in monomer units). The 11B1u exciton is also known as the (singlet) 'Frenkel' exciton, while the 21Ag exciton is also known as the (singlet) 'charge-transfer' exciton; see J. Chem. Phys. 129, 164716 (2008) or my book for further details.
The image shown below represents the formation of an exciton-polaron quasiparticle after photoexcitation of a conjugated polymer, caused by the coupling of the exciton to C-C bond vibrations. Ultrafast exciton-polaron formation causes ultrafast exciton decoherence and manifests itself as time-resolved fluorescence depolarization; see J. Chem. Phys. 148, 034901 (2018).
Developing theories of optical transitions in π-conjugated systems. The figure below shows the theoretical emission spectra of PPV as a function of torsonal disorder. The ratio of the 0-0 to 0-1 vibronic transitions is a measure of the average chromophore size, which decreases with increasing disorder; see J. Chem. Phys. 141, 164102 (2014).
Developing the density matrix renormalization group (DMRG) method for quantum chemistry and condensed matter physics. DMRG, matrix products states (MPS), and their associated time-dependent methods, are extremely powerful computational tools to solve one-dimensional quantum systems. As such, they are particularly suited to study conjugated polymers.
- Dr Max Marcus (Postdoctoral research associate): Singlet fission in carotenoids
- Darren Valentine (4th year DPhil student (submitted)): Singlet fission in carotenoids
- Laszlo Berencei (4th year DPhil student): Modelling charge transfer and dynamics in π-conjugated polymers
- Isabel Gonzalvez (3rd year DPhil student): Exciton dynamics and spectroscopy of π-conjugated polymers
- Dilhan Manawadu (2nd year DPhil student): Singlet fission in carotenoids
- Allison Arber (Part II student): Computing 2d-spectroscopy of π-conjugated polymers