arXiv subjects

Sumit Mazumdar

Publications and source records attributed to Sumit Mazumdar.

36 records · Page 2Linked to original sources

arXiv2015

Novel primary photoexcitations in $π$-conjugated donor-acceptor copolymers probed by transient magneto-photoinduced-absorption

The saga of the primary photoexcitations in $π$-conjugated polymers has been a source of extraordinary scientific curiosity that has lasted for more than three decades. From soliton excitations in trans-polyacetylene, to singlet and triplet excitons and polarons in other polymers, to charge transfer excitons in blends of polymers and fullerenes, the field has been rich with a variety of different photoexcitation species. Here we show the photogeneration of a novel primary intrachain photoexcitation species, namely the composite multi-exciton (CME) in $π$-conjugated donor-acceptor (DA)-copolymers used in organic photovoltaic (OPV) solar cells. We utilized the magnetic field response of the transient photoinduced absorption from sub-picosecond to millisecond to show in pristine DA-copolymer early photogeneration of the CME species that is composed of four coupled spin 1/2 particles, having unique optical and magnetic signatures. This species decomposes into two independent triplets in the microsecond time domain. Importantly in copolymer/fullerene blends the CME ionization generates photocarriers by a unique process that may enhance the photocurrent in OPV solar cells.

cond-mat.mes-hall↗

arXiv2015

Coulomb Enhanced Superconducting Pair Correlations in the Frustrated Quarter-Filled Band

A necessary condition for superconductivity (SC) driven by electron correlations is that electron-electron (e-e) interactions enhance superconducting pair-pair correlations, relative to the noninteracting limit. We report high-precision numerical calculations of the ground state within the frustrated two-dimensional (2D) Hubbard Hamiltonian for a wide range of carrier concentration $ρ$ (0 < $ρ$ <1) per site. We find that long range superconducting pair correlations are enhanced only for $ρ$ $\simeq$ 0.5. At all other fillings e-e interactions mostly suppress pair correlations. The enhancement of pair correlations is driven by the strong tendency to local singlet bond formation and spin gap (SG) in $ρ$ = 0.5, in lattices with quantum fluctuation. We also report determinantal quantum Monte Carlo (DQMC) calculations that are in strong agreement with our ground state results. Our work provides a key ingredient to the mechanism of SC in the 2D organic charge-transfer solids (CTS), and many other unconventional superconductors with frustrated crystal lattices and $ρ$ $\simeq$ 0.5, while explaining the absence of SC in structurally related materials with substantially different $ρ$.

cond-mat.supr-con↗

arXiv2015

Theory of Singlet Fission in Polyenes, Acene Crystals and Covalently Linked Acene Dimers

We report quadruple configuration interaction calculations within the extended Pariser$-$Parr$-$Pople Hamiltonian on the excited states of aggregates of polyenes, crystalline acenes, and covalently linked dimers of acene molecules. We determine the precise energy orderings and analyze the cluster wave functions in order to arrive at a comprehensive physical understanding of singlet fission in these diverse families of materials. Our computational approach allows us to retain a very large number of basis states and thereby obtain the correct relative energy orderings of one electron$-$one hole Frenkel and charge-transfer excitons versus intra- and intermolecular two electron$-$two hole triplet$-$triplet excited states. We show that from the energy orderings it is possible to understand the occurrence of singlet fission in polyene and acene crystals, as well as its near total absence in the covalently linked acene dimers. As in the acene crystals, singlet fission in the polyenes is a multichromophoric phenomenon, with the well-known 2$^1$A$_g^-$ playing no direct role. Intermolecular charge-transfer is essential for singlet fission in both acenes and polyenes, but because of subtle differences in the natures and orderings of the aggregate excited states, the mechanisms of singlet fission are slightly different in the two classes. We are thus able to give qualitative physical reasoning for the slower singlet fission in the polyenes, relative to that in crystalline pentacene. Our work also gives new insight into the complex exciton dynamics in tetracene crystals, which has been difficult to understand theoretically. Our large-scale many-body calculations provide us with the ability to understand the qualitative differences in the singlet fission yields and rates between different classes of $π$-conjugated materials.

cond-mat.str-el↗

arXiv2014

Theory of metal-intercalated phenacenes: Why molecular valence 3 is special

We develop a correlated-electron minimal model for the normal state of charged phenanthrene ions in the solid state, within the reduced space of the two lowest antibonding molecular orbitals of phenanthrene. Our model is general and can be easily extended to study the normal states of other polycyclic aromatic hydrocarbon superconductors. The main difference between our approach and previous correlated-electron theories of phenacenes is that our calculations are exact within the reduced basis space, albeit for finite clusters. The enhanced exchange of electron populations between these molecular orbitals, driven by Coulomb interactions over and above the bandwidth effects, gives a theoretical description of the phenanthrene trianions that is very different from previous predictions. Exact many-body finite cluster calculations show that while the systems with molecular charges of $-$1 and $-$2 are one- and two-band Mott-Hubbard semiconductors, respectively, molecular charge $-$3 gives two nearly $\frac{3}{4}$-filled bands, rather than a completely filled lower band and a $\frac{1}{2}$-filled upper band. The carrier density per active molecular orbital is thus nearly the same in the normal state of the superconducting aromatics and organic charge-transfer solids, and may be the key to understanding unconventional superconductivity in these molecular superconductors.

cond-mat.str-el↗

arXiv2012

Triplet excitations in carbon nanostructures

We show that the energy differences between the lowest optical singlet exciton and the lowest triplet exciton in semiconducting single-walled carbon nanotubes with diameter $\sim 1$ nm and graphene nanoribbons with widths $\sim 2$ nm are an order of magnitude smaller than in the $π$-conjugated polymer poly(para-phenylenevinylene). Our calculated energy gaps between the singlet and triplet excitons are in excellent agreement with the measured values in three different nanotubes with diameters close to 1 nm. The spatial extent of the triplet exciton is nearly the same as that of the singlet exciton in wide nanotubes and nanoribbons, in contrast to that in $π$-conjugated polymers, in which the triplet exciton exhibits strong spatial confinement. Weakly confined behavior of the triplet state begins in nanoribbons with widths as narrow as 2.5 times the graphene unit lattice vector. We discuss possible consequences of the small singlet-triplet energy difference in the carbon nanostructures on device applications.

cond-mat.mes-hall↗

arXiv2011

Is there a common theme behind the correlated-electron superconductivity in organic charge-transfer solids, cobaltates, spinels and fullerides?

We posit that there exist deep and fundamental relationships between the above seemingly very different materials. The carrier concentration-dependences of the electronic behavior in the conducting organic charge-transfer solids and layered cobaltates are very similar. These dependences can be explained within a single theoretical model, - the extended Hubbard Hamiltonian with significant nearest neighbor Coulomb repulsion. Interestingly, superconductivity in the cobaltates seems to be restricted to bandfilling exactly or close to one-quarter, as in the organics. We show that dynamic Jahn-Teller effects and the resultant orbital ordering can lead to 1/4-filled band descriptions for both superconducting spinels and fullerides, which show evidence for both strong electron-electron and electron-phonon interactions. The orbital orderings in antiferromagnetic lattice-expanded bcc M$_3$C$_{60}$ and the superconductor are different in our model. Strong correlations, quarter-filled band and lattice frustration are the common characteristics shared by these unusual superconductors.

cond-mat.str-el↗

arXiv2011

Similarities in electronic properties of organic charge-transfer solids and layered cobaltates

The apparently counterintuitive carrier concentration-dependent electronic properties of layered cobaltates have attracted wide interest. Here we point out that very similar carrier-concentration dependence has previously been noted in strongly correlated quasi-one dimensional (quasi-1D) organic charge-transfer solids. The normal states of both families can be understood, over the entire range of carrier concentration of interest, within the extended Hubbard Hamiltonian with significant intersite Coulomb interaction. As with the charge-transfer solids, superconductivity in the cobaltates appears to be limited to bandfilling of one-quarter. We point out further that there exist other families of correlated superconductors, such as spinels, where too strong correlations, geometric lattice frustration and bandfilling of one-quarter seem to be the essential features of the unconventional superconductors.

cond-mat.str-el↗

arXiv2008

Electron-electron interaction effects on the photophysics of metallic single-walled carbon nanotubes

Single-walled carbon nanotubes are strongly correlated systems with large Coulomb repulsion between two electrons occupying the same $p_z$ orbital. Within a molecular Hamiltonian appropriate for correlated $π$-electron systems, we show that optical excitations polarized parallel to the nanotube axes in the so-called metallic single-walled carbon nanotubes are to excitons. Our calculated absolute exciton energies in twelve different metallic single-walled carbon nanotubes, with diameters in the range 0.8 - 1.4 nm, are in nearly quantitative agreement with experimental results. We have also calculated the absorption spectrum for the (21,21) single-walled carbon nanotube in the E$_{22}$ region. Our calculated spectrum gives an excellent fit to the experimental absorption spectrum. In all cases our calculated exciton binding energies are only slightly smaller than those of semiconducting nanotubes with comparable diameters, in contradiction to results obtained within the {\it ab initio} approach, which predicts much smaller binding energies. We ascribe this difference to the difficulty of determining the behavior of systems with strong on-site Coulomb interactions within theories based on the density functional approach. As in the semiconducting nanotubes we predict in the metallic nanotubes a two-photon exciton above the lowest longitudinally polarized exciton that can be detected by ultrafast pump-probe spectroscopy. We also predict a subgap absorption polarized perpendicular to the nanotube axes below the lowest longitudinal exciton, blueshifted from the exact midgap by electron-electron interactions.

cond-mat.mtrl-sci↗

arXiv2008

Universality in the Photophysics of pi-Conjugated Polymers and Single-Walled Carbon Nanotubes

We describe both pi-conjugated polymers and semiconducting single-walled carbon nanotubes because of the remarkable similarities in their behavior under photoexcitation. The common themes between these two seemingly different classes of materials are pi-conjugation, quasi one-dimensionality, and strong Coulomb interactions. Theoretical understanding of both systems requires going beyond traditional band theory. We present our current understanding of the electronic structures and excited state absorptions in both systems within a common theoretical model. Our aim is to give physical interpretations of experiments that have been performed and to give guidance to future experimental work.

cond-mat.mtrl-sci↗

arXiv2008

Photophysics of charge-transfer excitons in thin films of π-conjugated polymers

We develop a theory of the electronic structure and photophysics of interacting chains of π- conjugated polymers to understand the differences between solutions and films. While photoexcitation generates only the intrachain exciton in solutions, the optical exciton as well as weakly allowed charge-transfer excitons are generated in films. We extend existing theories of the lowest polaronpair and charge-transfer excitons to obtain descriptions of the excited states of these interchain species, and show that a significant fraction of ultrafast photoinduced absorptions in films originate from the lowest charge-transfer exciton. Our proposed mechanism explains the simultaneous observation of polaronlike induced absorption features peculiar to films in ultrafast spectroscopy and the absence of mobile charge carriers as deduced from other experiments. We also show that there is a 1:1 correspondence between the essential states that describe the photophysics of single chains and of interacting chains that constitute thin films.

cond-mat.mtrl-sci↗

arXiv2007

Essential optical states in $π$-conjugated polymer thin films

We develop a theory of the electronic structure and photophysics of interacting chains of $π$-conjugated polymers to understand the differences between solutions and films. While photoexcitation generates only the exciton in solutions, the optical exciton as well as weakly allowed excimers are generated in films. Photoinduced absorption in films is primarily from the lowest excimer. We are also able to explain peculiarities associated with photoluminescence, including delayed photoluminescence and its quenching by electric field.

cond-mat.str-el↗

arXiv2007

pi-Electron theory of transverse optical excitons in semiconducting single-walled carbon nanotubes

We present a quantitative theory of optical absorption polarized transverse to the tube axes in semiconducting single-walled carbon nanotubes. Transverse optical absorption in semiconducting single-walled carbon nanotubes is to an exciton state that is strongly blueshifted, relative to the two lowest longitudinal excitons, by electron-electron interactions. The binding energy of the transverse exciton is considerably smaller than those of the longitudinal excitons. Electron-electron interactions also reduce the relative oscillator strength of the transverse optical absorption. Our theoretical results are in excellent agreement with recent experimental measurements in four chiral nanotubes.

cond-mat.mtrl-sci↗

arXiv2007

The Quantum Interference Effect Transistor: Principles and Perspectives

We give a detailed discussion of the Quantum Interference Effect Transistor (QuIET), a proposed device which exploits interference between electron paths through aromatic molecules to modulate current flow. In the off state, perfect destructive interference stemming from the molecular symmetry blocks current, while in the on state, current is allowed to flow by locally introducing either decoherence or elastic scattering. Details of a model calculation demonstrating the efficacy of the QuIET are presented, and various fabrication scenarios are proposed, including the possibility of using conducting polymers to connect the QuIET with multiple leads.

cond-mat.mes-hall↗

arXiv2007

Elucidation of the electronic structure of semiconducting single-walled carbon nanotubes by electroabsorption spectroscopy

We report benchmark calculations of electroabsorption in semiconducting single-walled carbon nanotubes to provide motivation to experimentalists to perform electroabsorption measurement on these systems. We show that electroabsorption can detect continuum bands in different energy manifolds, even as other nonlinear absorption measurements have failed to detect them. Direct determination of the binding energies of excitons in higher manifolds thereby becomes possible. We also find that electroabsorption can provide evidence for Fano-type coupling between the second exciton and the lowest continuum band states.

cond-mat.mtrl-sci↗

arXiv2006

Quantitative calculations of the excitonic energy spectra of semiconducting single-walled carbon nanotubes within a $π$-electron model

Using Coulomb correlation parameters appropriate for $π$-conjugated polymers (PCPs), and a nearest neighbor hopping integral that is arrived at by fitting the energy spectra of three zigzag semiconducting single-walled carbon nanotubes (S-SWCNTs), we are able to determine quantitatively the exciton energies and exciton binding energies of 29 S-SWCNTs within a semiempirical $π$-electron Hamiltonian that has been widely used for PCPs. Our work establishes the existence of a deep and fundamental relationship between PCPs and S-SWCNTs.

cond-mat.mtrl-sci↗

arXiv2004

Electron-electron interaction effects on optical excitations in semiconducting single-walled carbon nanotubes

We report correlated-electron calculations of optically excited states in ten semiconducting single-walled carbon nanotubes with a wide range of diameters. Optical excitation occurs to excitons whose binding energies decrease with the increasing nanotube diameter, and are smaller than the binding energy of an isolated strand of poly-(paraphenylene vinylene). The ratio of the energy of the second optical exciton polarized along the nanotube axis to that of the lowest exciton is smaller than the value predicted within single-particle theory. The experimentally observed weak photoluminescence is an intrinsic feature of semiconducting nanotubes, and is consequence of dipole-forbidden excitons occurring below the optical exciton.

cond-mat.mtrl-sci↗

arXiv2000

Electron correlation induced transverse delocalization and longitudinal confinement in excited states of phenyl-substituted polyacetylenes

Electron-electron interactions in general lead to both ground state and excited state confinement. We show, however, that in phenyl-substituted polyacetylenes electron-electron interactions cause enhanced delocalization of quasiparticles in the optically excited state from the backbone polyene chain into the phenyl groups, which in turn leads to enhanced confinement in the chain direction. This co-operative delocalization--confinement lowers the energy of the one-photon state and raises the relative energy of the lowest two-photon state. The two-photon state is slightly below the optical state in mono-phenyl substituted polyacetylenes, but above the optical state in di-phenyl substituted polyacetylenes, thereby explaining the strong photoluminescence of the latter class of materials. We present a detailed mechanism of the crossover in the energies of the one- and two-photon states in these systems. In addition, we calculate the optical absorption spectra over a wide wavelength region, and make specific predictions for the polarizations of low and high energy transitions that can be tested on oriented samples. Within existing theories of light emission from $π$-conjugated polymers, strong photoluminescence should be restricted to materials whose optical gaps are larger than that of trans-polyacetylene. The present work show that conceptually at least, it is possible to have light emission from systems with smaller optical gaps.

cond-mat.str-el↗

arXiv1999

Designing emissive conjugated polymers with small optical gaps: a step towards organic polymeric infrared lasers

We show that chemical modification of the trans-polyacetylene structure that involves substitution of the backbone hydrogen atoms with conjugated side groups, leads to reduction of the backbone bond alternation as well as screening of the effective Coulomb interaction. Consequently the optical gap of the substituted material is smaller than the parent polyene with the same backbone length, and the excited state ordering is conducive to efficient photoluminescence. The design of organic polymeric infrared lasers, in the ideal long chain limit, thereby becomes possible.

cond-mat↗