Second-order Cumulant Expansion Research Articles

Theory of 2D electronic spectroscopy of water soluble chlorophyll-binding protein (WSCP): Signatures of Chl b derivate.

We investigate how electronic excitations and subsequent dissipative dynamics in the water soluble chlorophyll-binding protein (WSCP) are connected to features in two-dimensional (2D) electronic spectra, thereby comparing results from our theoretical approach with experimental data from the literature. Our calculations rely on third-order response functions, which we derived from a second-order cumulant expansion of the dissipative dynamics involving the partial ordering prescription, assuming a fast vibrational relaxation in the potential energy surfaces of excitons. Depending on whether the WSCP complex containing a tetrameric arrangement of pigments composed of two dimers with weak excitonic coupling between them binds the chlorophyll variant Chl a or Chl b, the resulting linear absorption and circular dichroism spectra and particularly the 2D spectra exhibit substantial differences in line shapes. These differences between Chl a WSCP and Chl b WSCP cannot be explained by the slightly modified excitonic couplings within the two variants. In the case of Chl a WSCP, the assumption of equivalent dimer subunits facilitates a reproduction of substantial features from the experiment by the calculations. In contrast, for Chl b WSCP, we have to assume that the sample, in addition to Chl b dimers, contains a small but distinct fraction of chemically modified Chl b pigments. The existence of such Chl b derivates has been proposed by Pieper et al. [J. Phys. Chem. B 115, 4042 (2011)] based on low-temperature absorption and hole-burning spectroscopy. Here, we provide independent evidence.

Convergence criteria for single-step free-energy calculations: the relation between the Π bias measure and the sample variance.

Free energy calculations play a crucial role in simulating chemical processes, enzymatic reactions, and drug design. However, assessing the reliability and convergence of these calculations remains a challenge. This study focuses on single-step free-energy calculations using thermodynamic perturbation. It explores how the sample distributions influence the estimated results and evaluates the reliability of various convergence criteria, including Kofke's bias measure Π and the standard deviation of the energy difference ΔU, σ ΔU . The findings reveal that for Gaussian distributions, there is a straightforward relationship between Π and σ ΔU , free energies can be accurately approximated using a second-order cumulant expansion, and reliable results are attainable for σ ΔU up to 25 kcal mol-1. However, interpreting non-Gaussian distributions is more complex. If the distribution is skewed towards more positive values than a Gaussian, converging the free energy becomes easier, rendering standard convergence criteria overly stringent. Conversely, distributions that are skewed towards more negative values than a Gaussian present greater challenges in achieving convergence, making standard criteria unreliable. We propose a practical approach to assess the convergence of estimated free energies.

A superradiant two-level laser with intrinsic light force generated gain

The implementation of a superradiant laser as an active frequency standard is predicted to provide better short-term stability and robustness to thermal and mechanical fluctuations when compared to standard passive optical clocks. However, despite significant recent progress, the experimental realization of continuous wave superradiant lasing still remains an open challenge as it requires continuous loading, cooling, and pumping of active atoms within an optical resonator. Here we propose a new scenario for creating continuous gain by using optical forces acting on the states of a two-level atom via bichromatic coherent pumping of a cold atomic gas trapped inside a single-mode cavity. Analogous to atomic maser setups, tailored state-dependent forces are used to gather and concentrate excited-state atoms in regions of strong atom-cavity coupling while ground-state atoms are repelled. To facilitate numerical simulations of a sufficiently large atomic ensemble, we rely on a second-order cumulant expansion and describe the atomic motion in a semi-classical point-particle approximation subject to position-dependent light shifts which induce optical gradient forces along the cavity axis. We study minimal conditions on pump laser intensities and detunings required for collective superradiant emission. Balancing Doppler cooling and gain-induced heating we identify a parameter regime of a continuous narrow-band laser operation close to the bare atomic frequency.

Cumulant expansion in the Holstein model: Spectral functions and mobility

We examine the range of validity of the second-order cumulant expansion (CE) for the calculation of spectral functions, quasiparticle properties, and mobility of the Holstein polaron. We devise an efficient numerical implementation that allows us to make comparisons in a broad interval of temperature, electron-phonon coupling, and phonon frequency. For a benchmark, we use the dynamical mean-field theory which gives, as we have recently shown, rather accurate spectral functions in the whole parameter space, even in low dimensions. We find that in one dimension, the CE resolves well both the quasiparticle and the first satellite peak in a regime of intermediate coupling. At high temperatures, the charge mobility assumes a power law $\ensuremath{\mu}\ensuremath{\propto}{T}^{\ensuremath{-}2}$ in the limit of weak coupling and $\ensuremath{\mu}\ensuremath{\propto}{T}^{\ensuremath{-}3/2}$ for stronger coupling. We find that, for stronger coupling, the CE gives slightly better results than the self-consistent Migdal approximation (SCMA), while the one-shot Migdal approximation is appropriate only for a very weak electron-phonon interaction. We also analyze the atomic limit and the spectral sum rules. We derive an analytical expression for the moments in CE and find that they are exact up to the fourth order, as opposed to the SCMA where they are exact to the third order. Finally, we analyze the results in higher dimensions.

Spectral densities and absorption spectra of the core antenna complex CP43 from photosystem II.

Besides absorbing light, the core antenna complex CP43 of photosystem II is of great importance in transferring excitation energy from the antenna complexes to the reaction center. Excitation energies, spectral densities, and linear absorption spectra of the complex have been evaluated by a multiscale approach. In this scheme, quantum mechanics/molecular mechanics molecular dynamics simulations are performed employing the parameterized density functional tight binding (DFTB) while the time-dependent long-range-corrected DFTB scheme is applied for the excited state calculations. The obtained average spectral density of the CP43 complex shows a very good agreement with experimental results. Moreover, the excitonic Hamiltonian of the system along with the computed site-dependent spectral densities was used to determine the linear absorption. While a Redfield-like approximation has severe shortcomings in dealing with the CP43 complex due to quasi-degenerate states, the non-Markovian full second-order cumulant expansion formalism is able to overcome the drawbacks. Linear absorption spectra were obtained, which show a good agreement with the experimental counterparts at different temperatures. This study once more emphasizes that by combining diverse techniques from the areas of molecular dynamics simulations, quantum chemistry, and open quantum systems, it is possible to obtain first-principle results for photosynthetic complexes, which are in accord with experimental findings.

Molecular Origin of Driving-Dependent Friction in Fluids.

The friction coefficient of fluids may become a function of the velocity at increased external driving. This non-Newtonian behavior is of general theoretical interest and of great practical importance, for example, for the design of lubricants. Although the effect has been observed in large-scale atomistic simulations of bulk liquids, its theoretical formulation and microscopic origin are not well understood. Here, we use dissipation-corrected targeted molecular dynamics, which pulls apart two tagged liquid molecules in the presence of surrounding molecules, and analyze this nonequilibrium process via a generalized Langevin equation. The approach is based on a second-order cumulant expansion of Jarzynski's identity, which is shown to be valid for fluids and therefore allows for an exact computation of the friction profile as well of the underlying memory kernel. We show that velocity-dependent friction in fluids results from an intricate interplay of near-order structural effects and the non-Markovian behavior of the friction memory kernel. For complex fluids such as the model lubricant C40H82, the memory kernel exhibits a stretched-exponential long-time decay, which reflects the multitude of timescales of the system.

Many-body Green's function approaches to the doped Fröhlich solid: Exact solutions and anomalous mass enhancement

In polar semiconductors and insulators, the Fr\"ohlich interaction between electrons and long-wavelength longitudinal optical phonons induces a many-body renormalization of the carrier effective masses and the appearence of characteristic phonon sidebands in the spectral function, commonly dubbed 'polaron satellites'. The simplest model that captures these effects is the Fr\"ohlich model, whereby electrons in a parabolic band interact with a dispersionless longitudinal optical phonon. The Fr\"ohlich model has been employed in a number of seminal papers, from early perturbation-theory approaches to modern diagrammatic Monte Carlo calculations. One limitation of this model is that it focuses on undoped systems, thus ignoring carrier screening and Pauli blocking effects that are present in real experiments on doped samples. To overcome this limitation, we here extend the Fr\"ohlich model to the case of doped systems, and we provide exact solutions for the electron spectral function, mass enhancement, and polaron satellites. We perform the analysis using two approaches, namely Dyson's equation with the Fan-Migdal self-energy, and the second-order cumulant expansion. We find that these two approaches provide qualitatively different results. In particular, the Dyson's approach yields better quasiparticle masses and worse satellites, while the cumulant approach provides better satellite structures, at the price of worse quasiparticle masses. Both approaches yield an anomalous enhancement of the electron effective mass at finite doping levels, which in turn leads to a breakdown of the quasiparticle picture in a significant portion of the phase diagram.

Superradiant lasing in inhomogeneously broadened ensembles with spatially varying coupling.

Background: Theoretical studies of superradiant lasing on optical clock transitions predict a superb frequency accuracy and precision closely tied to the bare atomic linewidth. Such a superradiant laser is also robust against cavity fluctuations when the spectral width of the lasing mode is much larger than that of the atomic medium. Recent predictions suggest that this unique feature persists even for a hot and thus strongly broadened ensemble, provided the effective atom number is large enough. Methods: Here we use a second-order cumulant expansion approach to study the power, linewidth and lineshifts of such a superradiant laser as a function of the inhomogeneous width of the ensemble including variations of the spatial atom-field coupling within the resonator. Results: We present conditions on the atom numbers, the pump and coupling strengths required to reach the buildup of collective atomic coherence as well as scaling and limitations for the achievable laser linewidth. Conclusions: We show how sufficiently large numbers of atoms subject to strong optical pumping can induce synchronization of the atomic dipoles over a large bandwidth. This generates collective stimulated emission of light into the cavity mode leading to narrow-band laser emission at the average of the atomic frequency distribution. The linewidth is orders of magnitudes smaller than that of the cavity as well as the inhomogeneous gain broadening and exhibits reduced sensitivity to cavity frequency noise.

Superradiant lasing in inhomogeneously broadened ensembles with spatially varying coupling

Background: Theoretical studies of superradiant lasing on optical clock transitions predict a superb frequency accuracy and precision closely tied to the bare atomic linewidth. Such a superradiant laser is also robust against cavity fluctuations when the spectral width of the lasing mode is much larger than that of the atomic medium. Recent predictions suggest that this unique feature persists even for a hot and thus strongly broadened ensemble, provided the effective atom number is large enough. Methods: Here we use a second-order cumulant expansion approach to study the power, linewidth and lineshifts of such a superradiant laser as a function of the inhomogeneous width of the ensemble including variations of the spatial atom-field coupling within the resonator. Results: We present conditions on the atom numbers, the pump and coupling strengths required to reach the buildup of collective atomic coherence as well as scaling and limitations for the achievable laser linewidth. Conclusions: We show how sufficiently large numbers of atoms subject to strong optical pumping can induce synchronization of the atomic dipoles over a large bandwidth. This generates collective stimulated emission of light into the cavity mode leading to narrow-band laser emission at the average of the atomic frequency distribution. The linewidth is orders of magnitudes smaller than that of the cavity as well as the inhomogeneous gain broadening and exhibits reduced sensitivity to cavity frequency noise.

Reliable Predictions of Benzophenone Singlet-Triplet Transition Rates: A Second-Order Cumulant Approach.

Fermi golden rule and second-order cumulant expansion of the time-dependent density matrix have been used to compute from first principles the rate of intersystem crossing in benzophenone, using minimum-energy geometries and normal modes of vibrations computed at the TDDFT/CAM-B3LYP level. Both approaches yield reliable values of the S1 decay rate, the latter being almost in quantitative agreement with the results of time-dependent spectroscopic measurements (0.154 ps-1 observed vs 0.25 ps-1 predicted). The Fermi golden rule slightly overestimates the decay rate of S1 state (kd = 0.45 ps-1) but provides better insights into the chemico-physical parameters, which govern the transition from a thermally equilibrated population of S1, showing that the indirect mechanism is much faster than the direct one because of the vanishingly small Franck-Condon weighted density of states at ΔE of transition.

Simple charge transport model for efficient search of high-mobility organic semiconductor crystals

Search for materials with high charge mobilities among the plethora of synthesizable organic semiconductors is of paramount importance for organic electronics, and virtual screening is expected to guide and streamline this process. However, a model for rapid but reliable prediction of charge mobility in organic semiconductors is still lacking. To address this challenge, a simple “diffusion-of-delocalized-polaron” model is suggested in this study. It considers the most essential factors governing the charge transport: intermolecular electronic coupling, electron-phonon interaction, charge delocalization, static and dynamic disorder. The suggested model reproduces experimental charge mobilities in various organic semiconductors remarkably well, and significantly outperforms another approach previously used for screening of organic semiconductors – the Marcus model. Moreover, charge mobility values predicted by our model are closer to the experiment than those provided by the two state-of-the-art approaches – quantum nuclear tunneling model and second-order cumulant expansion of the density matrix – and are on par with the popular transient localization theory. It is thus anticipated that the suggested model is an efficient tool for the search of high-mobility materials, revealing of structure-mobility relationships and rational design of organic semiconductors. Its possible integration with crystal structure prediction can boost the development of organic electronics.

Charge Mobility Prediction in Organic Semiconductors: Comparison of Second-Order Cumulant Approximation and Transient Localization Theory

In the last years, several theoretical models for the simulation of charge transfer in organic semiconductors have been developed. Two particularly interesting approaches, because of their low computational cost and high accuracy, are the transient localization theory (TLT) and the second-order cumulant expansion of the density matrix (SOC). In this work, we apply these models for the evaluation of charge carrier mobility of four prototypical molecules, that is, tetracene, pentacene, picene, and rubrene. Their relative performances in reproducing experimental data are discussed, and their predictions are compared with the outcomes of semiclassical Marcus theory. We focus on a simplified framework for the SOC model, resorting to constant transfer integrals and time-averaged kinetic constants, showing that, despite the rather severe approximations introduced, the results are in good agreement with the TLT approach and experimental data. The temperature dependence of the mobility is also analyzed for pentace...

Lessons learned about steered molecular dynamics simulations and free energy calculations.

The calculation of free energy profiles is central in understanding differential enzymatic activity, for instance, involving chemical reactions that require QM-MM tools, ligand migration, and conformational rearrangements that can be modeled using classical potentials. The use of steered molecular dynamics (sMD) together with the Jarzynski equality is a popular approach in calculating free energy profiles. Here, we first briefly review the application of the Jarzynski equality to sMD simulations, then revisit the so-called stiff-spring approximation and the consequent expectation of Gaussian work distributions and, finally, reiterate the practical utility of the second-order cumulant expansion, as it coincides with the parametric maximum-likelihood estimator in this scenario. We illustrate this procedure using simulations of CO, both in aqueous solution and in a carbon nanotube as a model system for biologically relevant nanoheterogeneous environments. We conclude the use of the second-order cumulant expansion permits the use of faster pulling velocities in sMD simulations, without introducing bias due to large dispersion in the non-equilibrium work distribution.

Shattered time: can a dissipative time crystal survive many-body correlations?

We investigate the emergence of a time crystal (TC) in a driven dissipative many-body spin array. In this system the interplay between incoherent spin pumping and collective emission stabilizes a synchronized non-equilibrium steady state which in the thermodynamic limit features a self-generated time-periodic pattern imposed by collective elastic interactions. In contrast to prior realizations where the time symmetry is already broken by an external drive, here it is only spontaneously broken by the elastic exchange interactions and manifest in the two-time correlation spectrum. Employing a combination of exact numerical calculations and a second-order cumulant expansion, we investigate the impact of many-body correlations on the TC formation and establish a connection between the regime where it is stable and where the system features a slow growth rate of the mutual information. This observation allows us to conclude that the TC studied here is an emergent semi-classical out-of-equilibrium state of matter. We also confirm the rigidity of the TC to single-particle dephasing. Finally, we discuss an experimental implementation using long lived dipoles in an optical cavity.

Targeted Molecular Dynamics Calculations of Free Energy Profiles Using a Nonequilibrium Friction Correction.

As standard unbiased molecular dynamics (MD) simulations become impractical for sampling rare events, "targeted MD" employs a moving distance constraint to enforce rare transitions along some reaction coordinate x. To calculate free energy profiles from these nonequilibrium simulations via Δ G( x) = W( x) - Wdiss( x), apart from the (readily obtained) work W( x) performed on the system, the dissipated work Wdiss( x) is also required. By employing a second-order cumulant expansion of Jarzynski's equality combined with an analysis within Langevin theory, the dissipated work can be expressed via a nonequilibrium friction coefficient ΓNEQ( x) that may be calculated on-the-fly from constraint force fluctuations. Adopting the ion dissociation of NaCl in water as a test system, this friction correction is shown to result in accurate free energy profiles, even for a modest number of simulations and at high constraint velocities. As a bonus, the analysis of ΓNEQ( x) may yield valuable insight into the microscopic mechanism of friction.

Second-Order Cumulant Approach for the Evaluation of Anisotropic Hole Mobility in Organic Semiconductors

The anisotropic field effect mobilities of four prototypical semiconducting materials, that is, single crystals of pentacene, tetracene, picene, and rubrene, are evaluated by using the hopping model with time averaged rates obtained at the second-order cumulant (SOC) expansion of the time-dependent reduced density matrix. It is shown that the SOC approach allows for correcting the two known failures of the hopping mechanism: the highly overestimated mobilities provided by the Fermi golden rule and the incorrect temperature dependence predicted by the semiclassical Marcus’ approach.

Numerical simulation of the geometrical-optics reduction of CE2 and comparisons to quasilinear dynamics

Zonal flows have been observed to appear spontaneously from turbulence in a number of physical settings. A complete theory for their behavior is still lacking. Recently, a number of studies have investigated the dynamics of zonal flows using quasilinear (QL) theories and the statistical framework of a second-order cumulant expansion (CE2). A geometrical-optics (GO) reduction of CE2, derived under an assumption of separation of scales between the fluctuations and the zonal flow, is studied here numerically. The reduced model, CE2-GO, has a similar phase-space mathematical structure to the traditional wave-kinetic equation, but that wave-kinetic equation has been shown to fail to preserve enstrophy conservation and to exhibit an ultraviolet catastrophe. CE2-GO, in contrast, preserves nonlinear conservation of both energy and enstrophy. We show here how to retain these conservation properties in a pseudospectral simulation of CE2-GO. We then present nonlinear simulations of CE2-GO and compare with direct simulations of quasilinear (QL) dynamics. We find that CE2-GO retains some similarities to QL. The partitioning of energy that resides in the zonal flow is in good quantitative agreement between CE2-GO and QL. On the other hand, the length scale of the zonal flow does not follow the same qualitative trend in the two models. Overall, these simulations indicate that CE2-GO provides a simpler and more tractable statistical paradigm than CE2, but CE2-GO is missing important physics.

Hole Hopping Rates in Organic Semiconductors: A Second-Order Cumulant Approach.

Second-order cumulant expansion of the time dependent reduced density matrix has been employed to evaluate hole hopping rates in pentacene, tetracene, picene, and rubrene homodimers. The cumulant expansion is a full quantum mechanical approach, which enables the use of the whole set of nuclear coordinates in computations and the inclusion of both the effects of the equilibrium position displacements and of normal mode mixing upon hole transfer. The time dependent populations predicted by cumulant approach are in good agreement with those obtained by numerical solution of time dependent Schrödinger equation, even for ultrafast processes, where the Fermi Golden Rule fails.

Intersystem crossing rate dependent dual emission and phosphorescence from cyclometalated platinum complexes: a second order cumulant expansion based approach.

Rates of intersystem crossing (kISC) of two platinum(ii) complexes containing acetylacetonate (acac) and extended cyclometalated ppy (Hppy = 2-phenylpyridine) (1) and thpy (Hthpy = 2-(2' thienyl)pyridine) (2) ligands are calculated using the Condon approximation to the Golden Rule and employing the second-order cumulant expansion method. The emission wavelengths obtained at the RI-CC2 level for the lowest excited singlet (S1) and triplet (T1) states of the two complexes are well in agreement with the experimental results. Our analysis based on kISC evinces that the major pathway involved with the phosphorescence process in complex 1 arises from the S1 → T2 intersystem crossing while the S1 → T1 intersystem crossing is the key step towards the commencement of dual emission in complex 2. Furthermore, it is found that the different pathways are mostly guided by two factors namely, the energy gap and the spin-orbit interaction between the concerned states. Interestingly, the calculated kISC for complex 1 is found to be 107 times larger than that of complex 2, which suggests a rapid depletion of the S1 state population vis-à-vis radiative emission only by phosphorescence from the internally converted lowest excited triplet state while for complex 2, the relatively lower kISC is attributed to the dual emission from this complex.

Spectral line shapes in linear absorption and two-dimensional spectroscopy with skewed frequency distributions.

The effect of Gaussian dynamics on the line shapes in linear absorption and two-dimensional correlation spectroscopy is well understood as the second-order cumulant expansion provides exact spectra. Gaussian solvent dynamics can be well analyzed using slope line analysis of two-dimensional correlation spectra as a function of the waiting time between pump and probe fields. Non-Gaussian effects are not as well understood, even though these effects are common in nature. The interpretation of the spectra, thus far, relies on complex case to case analysis. We investigate spectra resulting from two physical mechanisms for non-Gaussian dynamics, one relying on the anharmonicity of the bath and the other on non-linear couplings between bath coordinates. These results are compared with outcomes from a simpler log-normal dynamics model. We find that the skewed spectral line shapes in all cases can be analyzed in terms of the log-normal model, with a minimal number of free parameters. The effect of log-normal dynamics on the spectral line shapes is analyzed in terms of frequency correlation functions, maxline slope analysis, and anti-diagonal linewidths. A triangular line shape is a telltale signature of the skewness induced by log-normal dynamics. We find that maxline slope analysis, as for Gaussian dynamics, is a good measure of the solvent dynamics for log-normal dynamics.