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In this work, we investigate anharmonic vibrational polaritons formed due to strong light–matter interactions in an optical cavity between radiation modes and anharmonic vibrations beyond the long-wavelength limit. We introduce a conceptually simple description of light–matter interactions, where spatially localized cavity radiation modes couple to localized vibrations. Within this theoretical framework, we employ self-consistent phonon theory and vibrational dynamical mean-field theory to efficiently simulate momentum-resolved vibrational-polariton spectra, including effects of anharmonicity. Numerical simulations in model systems demonstrate the accuracy and applicability of our approach. 

This study evaluates the precision of widely recognized quantum chemical methodologies, CCSD(T), DLPNO−CCSD(T), and localized ph-AFQMC, for determining the thermochemistry of main group elements. DLPNO−CCSD- (T) and localized ph-AFQMC, which o(er greater scalability compared to canonical CCSD(T), have emerged over the past decade as pivotal in producing precise benchmark chemical data. Our investigation includes closed-shell, neutral molecules, focusing on their heat of formation and atomization energy sourced from four specific small molecule data sets. First, we selected molecules from the G2 and G3 data sets, noted for their reliable experimental heat of formation data. Additionally, we incorporate molecules from the W4−11 and W4−17 sets, which provide high-level theoretical reference values for atomization energy at 0 K. Our findings reveal that both DLPNO−CCSD(T) and ph-AFQMC methods are capable of achieving a root-mean-square deviation of less than 1 kcal/mol across the combined data set, aligning with the threshold for chemical accuracy. Moreover, we make e(orts to confine the maximum deviations within 2 kcal/mol, a degree of precision that significantly broadens the applicability of these methods in fields such as biology and materials science. 

In this work we demonstrate that accurate ground state wave functions may be constructed for polarons in a fully ab initio setting across the wide range of couplings associated with both the large and small polaron limits. We present a single general unitary transformation approach which encompasses an ab initio version of the Lee-Low-Pines theory at weak coupling and the coherent state Landau-Pekar framework at strong coupling while interpolating between these limits in general cases. We show that perturbation theory around these limits may be performed in a facile manner to assess the accuracy of the approach, as well as provide an independent route to the ab initio properties of polarons. We test these ideas on the case of LiF, where the electron-polaron is expected to be large and relatively weakly coupled, while the hole-polaron is expected to be a strongly coupled small polaron. 

Abstract In this paper, we develop quantum dynamical methods capable of treating the dynamics of chemically reacting systems in an optical cavity in the vibrationally strong-coupling (VSC) limit at finite temperatures and in the presence of a dissipative solvent in both the few and many molecule limits. In the context of two simple models, we demonstrate how reactivity in thecollectiveVSC regime does not exhibit altered rate behavior in equilibrium but may exhibit resonant cavity modification of reactivity when the system is explicitly out of equilibrium. Our results suggest experimental protocols that may be used to modify reactivity in the collective regime and point to features not included in the models studied, which demand further scrutiny. 

We present a method for calculating first-order response properties in phaseless auxiliary field quantum Monte Carlo by applying automatic differentiation (AD). Biases and statistical efficiency of the resulting estimators are discussed. Our approach demonstrates that AD enables the calculation of reduced density matrices with the same computational cost scaling per sample as energy calculations, accompanied by a cost prefactor of less than four in our numerical calculations. We investigate the role of self-consistency and trial orbital choice in property calculations. We find that orbitals obtained using density functional theory perform well for the dipole moments of selected molecules compared to those optimized self-consistently. 

Abstract Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co₆Se₈(PEt₃)₆. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co₆Se₈] core while ligands function as an insulated shell.⁵⁹Co SSNMR measurements on the core and³¹P,¹³C on the ligands show that the neutral Co₆Se₈(PEt₃)₆is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co₆Se₈(PEt₃)₆]⁺¹is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.