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We report how the unique temporal and spectral features of pulsed entangled photons from a parametric downconversion source can be utilized for manipulating electronic excitations through the optimization of their spectral phase. A new comprehensive optimization protocol based on Bayesian optimization has been developed in this work to selectively excite electronic states accessible by two-photon absorption. Using our optimization method, the entangled two-photon absorption probability for a thiophene dendrimer can be enhanced by up to a factor of 20 while classical light turns out to be nonoptimizable. Moreover, the optimization involving photon entanglement enables selective excitation that would not be possible otherwise. In addition to optimization, we have explored entangled two-photon absorption in the small entanglement time limit showing that entangled light can excite molecular electronic states that are vanishingly small for classical light. We demonstrate these opportunities with an application to a thiophene dendrimer.

In this study, we investigate second- and third-harmonic generation processes in Au nanorod systems using the real-time time-dependent density functional tight binding method. Our study focuses on the computation of nonlinear signals based on the time dependent dipole response induced by linearly polarized laser pulses interacting with nanoparticles. We systematically explore the influence of various laser parameters, including pump intensity, duration, frequency, and polarization directions, on harmonic generation. We demonstrate all the results using Au nanorod dimer systems arranged in end-to-end configurations, and disrupting the spatial symmetry of regular single nanorod systems is crucial for second-harmonic generation processes. Furthermore, we study the impact of nanorod lengths, which lead to variable plasmon energies, on harmonic generation, and estimates of polarizabilities and hyper-polarizabilities are provided.

This study examines the Raman scattering and charge transfer properties of molecules adsorbed on the surface of a tetrahedral Au$_{120}$ nanoparticle based on the time-dependent density functional tight-binding (TD-DFTB) method. We study Raman scattering (SERS) enhancements for pyridine where the molecule is adsorbed either on the tip (V complex) or surface (S complex) of the nanoparticle. The scattering intensity is enhanced by a factor of 3-15 due to chemical effects while significantly larger enhancements (in the order of 10$^2$-10$^4$) are observed for plasmon resonance excitation at an energy of 2.5 eV depending on the adsorption site. Furthermore, we demonstrate charge transfer between the nanoparticle and a fullerene-based molecule after pulsed excitation of the plasmon resonance which shows how plasmon excitation can lead to negative molecular ion formation. All of these results are consistent with earlier studies using either TD-DFT theory or experimental measurements.

This paper provides new insights concerning the simulation of plasmon driven chemical reactions using real-time TDDFT based on the tight-binding electronic structure code DFTB+, with applications to the dissociation of H$_2$ on octahedral silver and gold nanoparticles with 19-489 atoms. A new component of these calculations involves sampling a 300 K canonical ensemble to determine the distribution of possible outcomes of the calculations, and with this approach we are able to determine the threshold for dissociation as a function of laser intensity, wavelength, and nanocluster size. We show that the threshold intensity varies as an inverse power of nanocluster size, which makes it possible to extrapolate the results to sizes that are more typical of experimental studies. The intensities obtained from this extrapolation are around a factor of 100 above powers used in the pulsed experiments. This is a closer comparison of theory and experiment than has been obtained in previous real-time simulations, and the remaining discrepancy can be understood in terms of electromagnetic hot spots that are associated with cluster formation. We also compare the influence of plasmon excitation versus inter-band excitation on reaction thresholds, revealing that for silver clusters plasmon excitation leads to lower thresholds, but for gold clusters, inter-band excitation is more effective. Our study also includes an analysis of charge transfer to and from the H$_2$ molecule, and a determination of orbital populations during and after the pulse, showing the correlation between metal excitations and the location of the antibonding level of H$_2$.

External driving of bath temperatures with a phase difference of a nonequilibrium quantum engine leads to the emergence of geometric effects on the thermodynamics. In this work, we modulate the amplitude of the external driving protocols by introducing envelope functions and study the role of geometric effects on the flux, noise and efficiency of a four-level driven quantum heat engine coupled with two thermal baths and a unimodal cavity. We observe that having a finite width of the modulation envelope introduces an additional control knob for studying the thermodynamics in the adiabatic limit. The optimization of the flux as well as the noise with respect to thermally induced quantum coherences becomes possible in presence of geometric effects, which is hitherto not possible with sinusoidal driving without an envelope. We also report the deviation of the slope and generation of an intercept in the standard expression for efficiency at maximum power as a function of Carnot efficiency in presence of geometric effects under the amplitude modulation. Further, a recently developed universal bound on the efficiency obtained from thermodynamic uncertainty relation is shown not to hold when a small width of the modulation envelope along with a large value of cavity temperature is maintained., Comment: 8 pages, 6 figures

We have constructed deep neural networks, which can map fluctuating photo-electron spectra obtained from noisy pulses to spectra from noise-free pulses. The network is trained on spectra from noisy pulses in combination with random Hamilton matrices, representing systems which could exist but do not necessarily exist. In [Giri et al., Phys. Rev. Lett. 124,113201 (2020)] we performed a purification of fluctuating spectra, that is mapping them to those from Fourier-limited Gaussian pulses. Here, we investigate the performance of such neural-network-based maps for predicting spectra of double pulses, pulses with a chirp and even partially-coherent pulses pulses from fluctuating spectra generated by noisy pulses. Secondly, we demonstrate that along with a purification of a fluctuating double-pulse spectrum, one can estimate the time-delay of the underlying double pulse, an attractive feature for single-shot spectra from SASE FELs. We demonstrate our approach with resonant two-photon ionization, a non-linear process, sensitive to details of the laser pulse., Comment: 10 pages, 9 figures

Photo-electron spectra obtained with intense pulses generated by free-electron lasers through self-amplified spontaneous emission are intrinsically noisy and vary from shot to shot. We extract the purified spectrum, corresponding to a Fourier-limited pulse, with the help of a deep neural network. It is trained on a huge number of spectra, which was made possible by an extremely efficient propagation of the Schr\"odinger equation with synthetic Hamilton matrices and random realizations of fluctuating pulses. We show that the trained network is sufficiently generic such that it can purify atomic or molecular spectra, dominated by resonant two- or three-photon ionization, non-linear processes which are particularly sensitive to pulse fluctuations. This is possible without training on those systems., Comment: 5 pages, 4 figures (application extended to a molecular system)

We propose a machine learning approach based on artificial neural network to gain faster insights on the role of geometric contributions to the nonequilibrium fluctuations of an adiabatically temperature-driven quantum heat engine coupled to a cavity. Using the artificial neural network we have explored the interplay between bunched and antibunched photon exchange statistics for different engine parameters. We report that beyond a pivotal cavity temperature, the Fano factor oscillates between giant and low values as a function of phase difference between the driving protocols. We further observe that the standard thermodynamic uncertainty relation is not valid when there are finite geometric contributions to the fluctuations, but holds true for zero phase difference even in presence of coherences., Comment: 8 pages, 8 figures. keywords: artificial intelligence, quantum thermodynamics, geometric phase, counting statistics, fluctuation theorem, thermodynamic uncertainty relation

We demonstrate that by changing the direction of the chirp in VUV pulses one can switch between excitation and ionization with very high contrast, if the carrier frequency of the light is resonant with two bound states. This is a surprising consequence if rapid adiabatic passage is extended to include transitions to the continuum. The chirp phase locks the linear combination of two resonantly coupled bound states whose ionization amplitudes interfere constructively or destructively depending on the chirp direction under suitable conditions. We derive the phenomenon in a minimal model and verify the effect with calculations for helium as a realistic example., Comment: 5 pages, 5 figures

By periodically driving the temperatures of reservoirs in quantum heat engines, geometric phase or Pancharatnam-Berry phase-like (PBp) effects in the thermodynamics can be observed. The PBp can be identified from a generating function (GF) method within an adiabatic quantum Markovian master equation formalism. The GF is shown not to lead to a standard open quantum system's fluctuation theorem in presence of phase-different modulations with an inapplicability in the use of the popular large deviation theory. Effect of coherences on the optimized value of the flux is nullified due to PBp contributions. The PBp causes the universality of the linear coefficient in the expansion of the efficiency at maximum power in terms of Carnot efficiency to be violated., Comment: 8 pages, 4 figures