arXiv subjects

Atandrita Bhattacharyya

Publications and source records attributed to Atandrita Bhattacharyya.

4 recordsLinked to original sources

arXiv2026

Persistent singlet electronic character in the multiexcitonic triplet-pair state of strongly coupled pentacene singlet fission dimers

Singlet fission converts an optically excited singlet state into a spin-entangled triplet pair state (TT$_1$)$^1$ that can, in principle, yield two free triplets for photovoltaics and/or a polarized high spin state for quantum technologies. Synthetically tunable templates suggest that the above photophysics is governed by a subtle but poorly understood interplay of molecular motifs, geometry and structural fluctuations. Here, we investigate the (TT$_1$)$^1$ state in a library of conformationally flexible pentacenic dimers, where a (TT$_1$)$^1$-specific near-IR spectral feature is readily available. Using a suite of polarization-controlled impulsive optical spectroscopies, we find that (TT$_1$)$^1$ formation is specific to planar conformations and is accompanied by large nuclear reorganization in the (TT$_1$)$^1$ photoproduct. Introducing polarization anisotropy to track the electronic character of the (TT$_1$)$^1$ species, supported by screened configuration interaction based electronic structure theory, we find that significant singlet-triplet electronic mixing is persistent throughout its evolution. This behavior is universal across diverse bridging motifs and indicates that, once the triplet pair is strongly bound, neither substantial nuclear reorganization nor structural fluctuations on longer timescales are sufficient to suppress persistent singlet-triplet electronic mixing, such that triplet-pair decorrelation is outcompeted by its decay. Our observations establish polarization-selective pump-probe and anisotropy as a direct optical probe of triplet pair decorrelation, complementary to spin-selective measurements at longer timescales.

physics.chem-ph↗

arXiv2026

State Localization and Selective Charge Filtering Near a Null Point

Null points in synthetically tunable molecular aggregates are predicted to generate flat energy bands analogous to those known in strongly correlated condensed-matter physics. For chemistry, null points provide a powerful design principle for photovoltaic materials with selective charge filtering similar to photosynthesis. However, null points have never been experimentally verified because their defining prediction - state localization with selective electron or hole transfer - has remained unobserved. Here, using a donor-acceptor dyad as a minimal model, we provide the first experimental observation of a null point. Impulsive pump-probe measurements reveal charge separation through a near-instantaneously generated locally excited-charge transfer (LE-CT) intermediate that emerges upon solvent stabilization of CT states. Polarization anisotropy directly reveals state localization and selective charge-filtering, spanning balanced electron-hole transfer to selective hole filtering consistent with synthetic design. A generalized vibronic theory of null points explains these observations and identifies the ideal synthetic parameters for achieving null points which are protected from the vibrational bath.

physics.chem-ph↗

arXiv2025

Intramolecular Singlet Fission Through a Coherently Coupled Excimer-like Intermediate

Singlet Fission (SF) into two triplets offers exciting avenues for high-efficiency photovoltaics and optically initializable qubits. While the chemical space of SF chromophores is ever-expanding, the mechanistic details of electronic-nuclear motions that dictate the photophysics are unclear. Rigid SF dimers with well-defined orientations are necessary to decipher such details. Here, using polarization-controlled white-light two-dimensional and pump-probe spectroscopies, we investigate a new class of contorted naphthalenediimide dimers, recently reported to have a favorable intramolecular SF (iSF) pathway. 2D cross-peaks directly identify the two Davydov components of the dimer along with strongly wavelength-dependent TT1 formation kinetics depending on which Davydov component is excited, implicating a coherently coupled intermediate that mediates iSF. Enhanced quantum beats in the TT1 photoproduct suggest that inter-chromophore twisting and ruffling motions drive the ~200 fs evolution towards an excimer-like intermediate and its subsequent ~2 ps relaxation to the TT1 photoproduct. Polarization anisotropy directly tracks electronic motion during these steps and reveals surprisingly minimal electronic reorientation with significant singlet-triplet mixing throughout the nuclear evolution away from the Franck-Condon geometry towards relaxed TT1. The observations of coherent excimer-like intermediate and significant singlet-triplet mixing throughout the iSF process need to be carefully accounted for in the synthetic design and electronic structure models for iSF dimers aiming for long-lived high-spin correlated triplets.

physics.chem-ph↗

arXiv2023

Low and High Frequency Vibrations Synergistically Enhance Singlet Exciton Fission Through Robust Vibronic Resonances

Singlet exciton fission (SEF) is initiated by ultrafast internal conversion of a singlet exciton into a correlated triplet pair (TT)1. The `reaction coordinates' for ultrafast SEF even in archetypal systems such as pentacene thin film remain unclear with synthetic design principles broadly relying on tailoring electronic couplings to achieve new templates for efficient SEF materials. Spectroscopic detection of vibrational coherences in the (TT)1 photoproduct has motivated theoretical investigations into a possible role of vibronic resonance in driving SEF, akin to that reported in several photosynthetic proteins. However, a precise understanding of how prominent low-frequency vibrations and their modulation of intermolecular orbital overlaps, equally prominent high-frequency vibrations, and order of magnitude larger Huang-Rhys factors in SEF chromophores compared to photosynthetic pigments, collectively influence the mechanistic details of SEF remains starkly lacking. Here we address this gap and identify previously unrecognized effects which are quite contrasting from those known in photosynthesis excitons, and vitally enhance non-adiabatic internal conversion in SEF. Our findings have direct implications for the broad experimental interest in synthetically tailoring molecules to promote vibronically enhanced internal conversion.

physics.chem-ph↗