arXiv subjects

Satish Patil

Publications and source records attributed to Satish Patil.

6 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↗

arXiv2023

Heterogeneous Singlet Fission in a Covalently Linked Pentacene Dimer

Molecular dimers are widely utilized as a tool to investigate the structure-property relationships behind the complex photophysical processes of condensed-phase systems, where structural tuning remains a challenge. This approach often implicitly treats the dimers as static, with their relevant state energies and couplings determined by their optimized geometry. Here, we consider the shortcomings of this approach: dimers are more accurately treated as dynamic model systems, with the potential for significant conformational heterogeneity that evolves in time and is intimately connected with interchromophore coupling strengths. We highlight this concept in the singlet fission dynamics of a pentacene dimer that is covalently linked through phenyl-diketopyrrolopyrrole and acetylene bridges. Unrestricted rotations lead to a vast array of rotational conformers in the ground state. Consequently, we find that every step in the cascade of singlet fission processes - triplet-pair formation from S1, triplet-pair recombination, spin evolution within the pair, and free triplet formation - is qualitatively and quantitatively altered by the conformer geometry. At room temperature, we find evidence of dynamic interconversion between conformers on the multiple TT surfaces. Measurements in frozen solution at 150 K emphasize the significance of static disorder. Our data reveals the presence of sub-populations that result in excitation-dependent electron spin polarization. These phenomena demand consideration of multidimensional potential energy surfaces that define multiple sub-ensembles in the excited state, a picture we refer to as heterogeneous singlet fission. More broadly, our results call into question the general static approach to molecular dimer photophysics, that each step in consecutive excited-state relaxation pathways can be delineated with a single, unique rate constant and yield.

physics.chem-ph↗

arXiv2019

Observation of excess resistance anomaly at resistive transitions in Ag/Au nanostructures

The resistive transition in nanocomposite films of silver (Ag) nanoclusters of ~ 1 nm diameter embedded in gold (Au) matrix exhibits an anomalous resistance peak at the onset of the transition, even for transition temperatures as high as 260 K. The maximum value of the resistance ranges between ~ 30% - 300% above that of the normal state depending on devices as well as lead configuration within a single device. The excess resistance regime was observed in about 10% of the devices, and extends from ~ 10 - 100 K. Application of magnetic field of 9 T was found to partially suppress the excess resistance. From the critical current behavior, as well as negative differential resistance in the current-voltage characteristics, we discuss the possibility of interacting phase slip centers and alternate physical scenarios that may cause the excess resistance in our system.

cond-mat.supr-con↗

arXiv2019

Current-voltage characteristics in Ag/Au nanostructures at resistive transitions

Transitions to immeasurably small electrical resistance in thin films of Ag/Au nanostructure-based films have generated significant interest because such transitions can occur even at ambient temperature and pressure. While the zero-bias resistance and magnetic transition in these films have been reported recently, the non-equilibrium current-voltage ($I-V$) transport characteristics at the transition remains unexplored. Here we report the $I-V$ characteristics at zero magnetic field of a prototypical Ag/Au nanocluster film close to its resistivity transition at the critical temperature $T_{C}$ of $\approx160$ K. The $I-V$ characteristics become strongly hysteretic close to the transition and exhibit a temperature-dependent critical current scale beyond which the resistance increases rapidly. Intriguingly, the non-equilibrium transport regime consists of a series of nearly equispaced resistance steps when the drive current exceeds the critical current. We have discussed the similarity of these observations with resistive transitions in ultra-thin superconducting wires via phase slip centres.

cond-mat.mes-hall↗

arXiv2019

Coexistence of Diamagnetism and Vanishingly Small Electrical Resistance at Ambient Temperature and Pressure in Nanostructures

The great practical utility has motivated extensive efforts to discover ultra-low resistance electrical conductors and superconductors in ambience. Here we report the observation of vanishingly small electrical resistance at the ambient temperature and pressure conditions in films and pellets of a nanostructured material that is composed of silver particles embedded into a gold matrix. Upon cooling below a sample-specific temperature scale ($T_{C}$) as high as $286$ K, the film resistance drops below $\sim 2μΩ$, being limited by measurement uncertainty. The corresponding resistivity ($\sim 10^{-12}$ $Ω$.m) is at least four orders of magnitude below that of elemental noble metals, such as gold, silver or copper. Furthermore, the samples become strongly diamagnetic below $T_{C}$, with volume susceptibilities as low as -0.056. We additionally describe methods to tune $T_{C}$ to temperatures much higher than room temperature.

cond-mat.supr-con↗

arXiv2014

Room Temperature Band-like Transport and Hall Effect in a High Mobility Ambipolar Polymer

The advent of new-class of high-mobility semiconducting polymers opens up a window to address fundamental issues in electrical transport mechanism such as hopping between localized states versus extended state conduction. Here, we investigate the origin of ultra-low degree of disorder (~ 16 meV) and band-like negative temperature (T) coefficient of the field effect electron mobility in a high performance diketopyrrolopyrrole (DPP)-based semiconducting polymer. Models based on the framework of mobility edge (ME) with exponential density of states are invoked to explain the trends in transport. The temperature window over which the system demonstrates de-localized transport was tuned by a systematic introduction of disorder at the transport interface. Additionally, the Hall mobility extracted from Hall-voltage measurements in these devices was found to be comparable to field effect mobility in the high T band-like regime. Comprehensive studies with different combinations of dielectrics and semiconductors demonstrate the effectiveness of rationale molecular design which emphasizes uniform-energetic landscape and low re-organization energy.

cond-mat.mtrl-sci↗