arXiv subjects

Arpan Kundu

Publications and source records attributed to Arpan Kundu.

15 recordsLinked to original sources

arXiv2026

First-principles cumulant approach to the vibronic structure of spin defects

Color centers in wide-band-gap semiconductors are leading platforms for solid-state quantum technologies, yet a quantitative description of their vibronic structure has remained elusive due to the complexity of multi-phonon processes in localized defect states. Here we present a first-principles Green's function framework based on the retarded cumulant ansatz (RCA) to describe electron-phonon interactions in spin defects; our approach goes beyond the adiabatic and lowest-order perturbation theory approximations underlying widely used approaches. Applied to the negatively charged nitrogen-vacancy (NV$^-$) center in diamond, our method reveals that multi-phonon satellites persist over a 400 meV energy window even at zero temperature, driven by quantum zero-point fluctuations. We demonstrate that accurate spectral functions require mode-, momentum-, spin-, and orbital-resolved electron-phonon matrix elements sampled across the full Brillouin zone, to account for hybridized and propagating phonon channels. We find that the vibronic structure of the NV$^-$ center exhibits strong spin and orbital anisotropy, with different orbitals coupling to qualitatively distinct parts of the phonon spectrum, and spin-selective coupling affecting both sideband positions and intensities.

cond-mat.mtrl-sci↗

arXiv2026

RLEASE: Reinforcement Learning Efficient Active Space Engine

Selecting the active space for multireference electronic-structure calculations is a long-standing bottleneck that often requires expert chemical intuition and costly trial-and-error. We introduce RLEASE (Reinforcement Learning Efficient Active Space Engine), a low-cost method for automatic, geometry-dependent active-space selection. A neural network predicts per-orbital diagnostic scores ($\hat{s}_{1}$) from inexpensive Hartree-Fock orbital descriptors, and a learned threshold partitions orbitals into active and inactive sets. The threshold policy is optimized with proximal policy optimization, using the discrepancy between sc-NEVPT2 energies computed with the selected active space and DMRG reference energies as the reward. After training, the same RLEASE-selected active spaces can be used with multireference perturbation theory or composite coupled-cluster energy estimators. Despite being trained on a small set of molecules and geometries, RLEASE transfers to chemically diverse test systems, producing compact active spaces and competitive potential-energy surfaces relative to established entropy-based selectors. Because deployment requires only inexpensive orbital descriptors and neural-network inference, RLEASE enables high-throughput multireference workflows without molecule-specific retraining or target-system pilot DMRG calculations.

physics.chem-ph↗

arXiv2025

Defects at Play: Shaping the Photophysics and Photochemistry of Ice

The mechanisms by which light interacts with ice and the impact of photo-induced reactions are central to our understanding of environmental, atmospheric and astrophysical processes. However, a microscopic description of the photoproducts originating from UV absorption and emission processes has remained elusive. Here we explore the photochemistry of ice using time-dependent hybrid density functional theory on various models of pristine and defective ice Ih. Our investigation of the excited state potential energy surface of the crystal shows that UV absorption can lead to the formation of hydronium ions, hydroxyl radicals and excess electrons. One of the dominant mechanisms of decay from the excited to the ground-state involves the recombination of the electron with the hydroxyl radical yielding hydronium-hydroxide ion-pairs. We find that the details of this charge recombination process sensitively depend on the presence of defects in the lattice, such as vacancies and pre-existing photoproducts. We also observe the formation of Bjerrum defects following UV absorption; we suggest that, together with hydroxide anions, they are likely responsible for prominent features experimentally detected in long UV exposure absorption spectra, remarkably red-shifted relative to short exposure spectra. Our results highlight the key role of defects in determining the onset of absorption and emission processes in ice.

physics.chem-ph↗

arXiv2024

Designing Optically Addressable Nitrogen-Vacancy Centers in Ultra-Small Nanodiamonds: Insights from First-Principles Calculations

Ultrasmall nanodiamonds (USNDs) are promising platforms for fluorescent and quantum sensing applications. Here we present first-principles electronic structure calculations of color centers in USNDs, specifically the nitrogen-vacancy (NV-) and we investigate their optical addressability as a function of the surface termination. We consider both isolated nanoparticles and arrays of USNDs with different degrees of packing, and we include quantum vibronic effects in our analysis, using stochastic methods. We find that the NV in USNDs can be stabilized in a negative charge state if the nanoparticles are terminated by fluorine, hydroxyl, and ether. While fluorine terminations can be used for fluorescent bio-tags, we suggest that hydroxyl and ether terminations are beneficial for quantum sensing applications. We also find that the NV- can be stabilized in arrays of USNDs when inter-particle separations are larger than the diameter of the nanoparticle. Interestingly, the phonon renormalizations of single-particle energy levels found in arrays contribute to the charge stability of negatively charged NV centers.

physics.comp-ph↗

arXiv2024

Nuclear Quantum Effects on the Electronic Structure of Water and Ice

The electronic properties and optical response of ice and water are intricately shaped by their molecular structure, including the quantum mechanical nature of hydrogen atoms. In spite of numerous studies appeared over decades, a comprehensive understanding of the effect of the nuclear quantum motion on the electronic structure of water and ice at finite temperatures remains elusive. Here, we utilize molecular simulations that harness the efficiency of machine-learning potentials and many-body perturbation theory to assess the impact of nuclear quantum effects on the electronic structure of water and hexagonal ice. By comparing the results of path-integral and classical simulations, we find that including nuclear quantum effects leads to a larger renormalization of the fundamental gap of ice, compared to that of water, eventually leading to a comparable gap in the two systems, consistent with experimental estimates. Our calculations suggest that the quantum fluctuations responsible for an increased delocalization of protons in ice, relative to water, are a key factor leading to the enhancement of nuclear quantum effects on the electronic structure of ice.

physics.chem-ph↗

arXiv2024

Quantum Vibronic Effects on the Excitation Energies of the Nitrogen-Vacancy Center in Diamond

We investigate the impact of quantum vibronic coupling on the electronic properties of solid-state spin defects using stochastic methods and first principles molecular dynamics with a quantum thermostat. Focusing on the negatively charged nitrogen-vacancy center in diamond as an exemplary case, we found a significant dynamic Jahn-Teller splitting of the doubly degenerate single-particle levels within the diamond's band gap, even at 0 K, with a magnitude exceeding 180 meV. This pronounced splitting leads to substantial renormalizations of these levels and subsequently, of the vertical excitation energies of the doubly degenerate singlet and triplet excited states. Our findings underscore the pressing need to incorporate quantum vibronic effects in first-principles calculations, particularly when comparing computed vertical excitation energies with experimental data. Our study also reveals the efficiency of stochastic thermal line sampling for studying phonon renormalizations of solid-state spin defects.

physics.comp-ph↗

arXiv2023

A Brief Review on the Asymptotic Symmetries of Gravity in Higher Dimensions

In this brief review, we report on the status of asymptotic symmetries of gravity corresponding to the class of metrices named asymptotically flat spacetimes in higher (d > 4) dimensions. We discuss the consequences of these symmetries both in classical and quantum theories. We also discuss the open issues in these aspects.

hep-th↗

arXiv2023

Quantum vibronic effects on the electronic properties of molecular crystals

We present a study of molecular crystals, focused on the effect of nuclear quantum motion and anharmonicity on their electronic properties. We consider a system composed of relatively rigid molecules, a diamondoid crystal, and one composed of floppier molecules, NAI-DMAC, a thermally activated delayed fluorescence compound. We compute fundamental electronic gaps at the DFT level of theory, with the PBE and SCAN functionals, by coupling first-principles molecular dynamics with a nuclear quantum thermostat. We find a sizable zero-point-renormalization (ZPR) of the band gaps, which is much larger in the case of diamondoids (~ 0.6 eV) than for NAI-DMAC (~ 0.22 eV). We show that the frozen phonon (FP) approximation, which neglects inter-molecular anharmonic effects, leads to a large error (~ 50%) in the calculation of the band gap ZPR. Instead, when using a stochastic method, we obtain results in good agreement with those of our quantum simulations for the diamondoid crystal. However, the agreement is worse for NAI-DMAC where intra-molecular anharmonicities contribute to the ZPR. Our results highlight the importance of accurately including nuclear and anharmonic quantum effects to predict the electronic properties of molecular crystals.

physics.comp-ph↗

arXiv2022

Generalized BMS algebra in higher even dimensions

We revisit the status of asymptotic symmetries in higher even dimensions and propose a definition of superrotation charge beyond linearized gravity. We prove that there is a well-defined spacetime action of the superrotation charge on the space of asymptotically flat geometries. Additionally, we demonstrate that the Ward identity associated with superrotation charges follows from the subleading soft graviton theorem, which is a universal constraint (in $d> 4$) along with the leading soft graviton theorem.

hep-th↗

arXiv2022

Computational protocol to evaluate electron-phonon interactions within density matrix perturbation theory

We present a computational protocol, based on density matrix perturbation theory, to obtain non-adiabatic, frequency-dependent electron-phonon self-energies for molecules and solids. Our approach enables the evaluation of electron-phonon interaction using hybrid functionals, for spin-polarized systems, and the computational overhead to include dynamical and non-adiabatic terms in the evaluation of electron-phonon self-energies is negligible. We discuss results for molecules, as well as pristine and defective solids.

cond-mat.mtrl-sci↗

arXiv2021

Combined first-principles calculations of electron-electron and electron-phonon self-energies in condensed systems

We present a method to efficiently combine the computation of electron-electron and electron-phonon self-energies, which enables the evaluation of electron-phonon coupling at the $G_0W_0$ level of theory for systems with hundreds of atoms. In addition, our approach, which is a generalization of a method recently proposed for molecules [J. Chem. Theory Comput. 2018, 14, 6269-6275], enables the inclusion of non-adiabatic and temperature effects at no additional computational cost. We present results for diamond and defects in diamond and discuss the importance of numerically accurate $G_0W_0$ band structures to obtain robust predictions of zero point renormalization (ZPR) of band gaps, and of the inclusion of non-adiabatic effect to accurately compute the ZPR of defect states in the band gap.

cond-mat.mtrl-sci↗

arXiv2021

Quantum vibronic effects on the electronic properties of solid and molecular carbon

We study the effect of quantum vibronic coupling on the electronic properties of carbon allotropes, including molecules and solids, by combining path integral first principles molecular dynamics (FPMD) with a colored noise thermostat. In addition to avoiding several approximations commonly adopted in calculations of electron-phonon coupling, our approach only adds a moderate computational cost to FPMD simulations and hence it is applicable to large supercells, such as those required to describe amorphous solids. We predict the effect of electron-phonon coupling on the fundamental gap of amorphous carbon, and we show that in diamond the zero-phonon renormalization of the band gap is larger than previously reported.

cond-mat.mtrl-sci↗

arXiv2020

Generalized BMS Algebra at Timelike Infinity

BMS group (and it's various generalizations) at null infinity have been studied extensively in the literature as the symmetry group of asymptotically flat spacetimes. The intricate relationship between soft theorems and the BMS symmetries have also motivated the definition of such asymptotic symmetries to time-like infinity. Although the vector fields that generate the (generalized) BMS algebra at time-like infinity was defined in the literature, the algebra has not been investigated. In this paper, we fill this gap. We show that the super-translations and vector fields that generate sphere diffeomorphisms close under the modified Lie bracket proposed by Barnich et al.

hep-th↗

arXiv2018

Double Soft Graviton Theorems and BMS Symmetries

It is now well understood that Ward identities associated to the (extended) BMS algebra are equivalent to single soft graviton theorems. In this work, we show that if we consider nested Ward identities constructed out of two BMS charges, a class of double soft factorization theorems can be recovered. By making connections with earlier works in the literature, we argue that at the sub-leading order, these double soft graviton theorems are the so-called consecutive double soft graviton theorems. We also show how these nested Ward identities can be understood as Ward identities associated to BMS symmetries in scattering states defined around (non-Fock) vacua parametrized by supertranslations or superrotations.

hep-th↗

arXiv2016

Magnetothermoelectric effects in graphene and their dependence on scatterer concentration, magnetic field and band gap

Using a semiclassical Boltzmann transport equation (BTE) approach, we derive analytical expressions for electric and thermoelectric transport coefficients of graphene in the presence and absence of a magnetic field. Scattering due to acoustic phonons, charged impurities and vacancies are considered in the model. Seebeck ($S_{xx}$) and Nernst ($N$) coefficients have been evaluated as functions of carrier density, temperature, scatterer concentration, magnetic field and induced band gap, and the results are compared with experimental data. $S_{xx}$ is an odd function of Fermi energy while $N$ is an even function, as observed in experiments. The peaks of both coefficients are found to increase with decreasing scatterer concentration and increasing temperature. Furthermore, opening a band gap decreases $N$ but increases $S_{xx}$. Applying a magnetic field introduces an asymmetry in the variation of $S_{xx}$ with Fermi energy across the Dirac point. The formalism is more accurate and computationally efficient than the conventional Green's function approach used to model transport coefficients and can be used to explore transport properties of other exotic materials.

cond-mat.mtrl-sci↗