Vladimir Y. Chernyak

Loop series for discrete statistical models on graphs

In this paper we present the derivation details, logic, and motivation for the three loop calculus introduced in Chertkov and Chernyak (2006xa0Phys.xa0Rev.xa0Exa073xa0065102(R)). Generating functions for each of the three interrelated discrete statistical models are expressed in terms of a finite series. The first term in the series corresponds to the Bethe–Peierls belief–propagation (BP) contribution; the other terms are labelled by loops on the factor graph. All loop contributions are simple rational functions of spin correlation functions calculated within the BP approach. We discuss two alternative derivations of the loop series. One approach implements a set of local auxiliary integrations over continuous fields with the BP contribution corresponding to an integrand saddle-point value. The integrals are replaced by sums in the complementary approach, briefly explained in Chertkov and Chernyakxa0(2006xa0Phys.xa0Rev.xa0Exa073xa0065102(R)). Local gauge symmetry transformations that clarify an important invariant feature of the BP solution are revealed in both approaches. The individual terms change under the gauge transformation while the partition function remains invariant. The requirement for all individual terms to be nonzero only for closed loops in the factor graph (as opposed to paths with loose ends) is equivalent to fixing the first term in the series to be exactly equal to the BP contribution. Further applications of the loop calculus to problems in statistical physics, computer and information sciences are discussed.

Nonadiabatic Excited-State Molecular Dynamics Modeling of Photoinduced Dynamics in Conjugated Molecules

Nonadiabatic dynamics generally defines the entire evolution of electronic excitations in optically active molecular materials. It is commonly associated with a number of fundamental and complex processes such as intraband relaxation, energy transfer, and light harvesting influenced by the spatial evolution of excitations and transformation of photoexcitation energy into electrical energy via charge separation (e.g., charge injection at interfaces). To treat ultrafast excited-state dynamics and exciton/charge transport we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework incorporating quantum transitions. Our calculations rely on the use of the Collective Electronic Oscillator (CEO) package accounting for many-body effects and actual potential energy surfaces of the excited states combined with Tullys fewest switches algorithm for surface hopping for probing nonadiabatic processes. This method is applied to model the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene, PPV). Our analysis shows intricate details of photoinduced vibronic relaxation and identifies specific slow and fast nuclear motions that are strongly coupled to the electronic degrees of freedom, namely, torsion and bond length alternation, respectively. Nonadiabatic relaxation of the highly excited mA(g) state is predicted to occur on a femtosecond time scale at room temperature and on a picosecond time scale at low temperature.

Path-integral analysis of fluctuation theorems for general Langevin processes

We examine classical, transient fluctuation theorems within the unifying framework of Langevin dynamics. We explicitly distinguish between the effects of non-conservative forces that violate detailed balance, and non-autonomous dynamics arising from the variation of an external parameter. When both these sources of nonequilibrium behaviour are present, there naturally arise two distinct fluctuation theorems.

Nonadiabatic excited-state molecular dynamics: Numerical tests of convergence and parameters

Nonadiabatic molecular dynamics simulations, involving multiple Born-Oppenheimer potential energy surfaces, often require a large number of independent trajectories in order to achieve the desired convergence of the results, and simulation relies on different parameters that should be tested and compared. In addition to influencing the speed of the simulation, the chosen parameters combined with the frequently reduced number of trajectories can sometimes lead to unanticipated changes in the accuracy of the simulated dynamics. We have previously developed a nonadiabatic excited state molecular dynamics methodology employing Tullys fewest switches surface hopping algorithm. In this study, we seek to investigate the impact of the number of trajectories and the various parameters on the simulation of the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene) within our developed framework. Various user-defined parameters are analyzed: classical and quantum integration time steps, the value of the friction coefficient for Langevin dynamics, and the initial seed used for stochastic thermostat and hopping algorithms. Common approximations such as reduced number of nonadiabatic coupling terms and the classical path approximation are also investigated. Our analysis shows that, at least for the considered molecular system, a minimum of ~400 independent trajectories should be calculated in order to achieve statistical averaging necessary for convergence of the calculated relaxation timescales.

Excitonic effects in a time-dependent density functional theory.

Excited state properties of one-dimensional molecular materials are dominated by many-body interactions resulting in strongly bound confined excitons. These effects cannot be neglected or treated as a small perturbation and should be appropriately accounted for by electronic structure methodologies. We use adiabatic time-dependent density functional theory to investigate the electronic structure of one-dimensional organic semiconductors, conjugated polymers. Various commonly used functionals are applied to calculate the lowest singlet and triplet state energies and oscillator strengths of the poly(phenylenevinylene) and ladder-type (poly)(para-phenylene) oligomers. Local density approximations and gradient-corrected functionals cannot describe bound excitonic states due to lack of an effective attractive Coulomb interaction between photoexcited electrons and holes. In contrast, hybrid density functionals, which include long-range nonlocal and nonadiabatic corrections in a form of a fraction of Hartree-Fock exchange, are able to reproduce the excitonic effects. The resulting finite exciton sizes are strongly dependent on the amount of the orbital exchange included in the functional.

Loop calculus in statistical physics and information science

Considering a discrete and finite statistical model of a general position we introduce an exact expression for the partition function in terms of a finite series. The leading term in the series is the Bethe-Peierls (belief propagation) (BP) contribution; the rest are expressed as loop contributions on the factor graph and calculated directly using the BP solution. The series unveils a small parameter that often makes the BP approximation so successful. Applications of the loop calculus in statistical physics and information science are discussed.

Diagnosis of weaknesses in modern error correction codes: A physics approach

One of the main obstacles to the wider use of the modern error-correction codes is that, due to the complex behavior of their decoding algorithms, no systematic method which would allow characterization of the bit-error-rate (BER) is known. This is especially true at the weak noise where many systems operate and where coding performance is difficult to estimate because of the diminishingly small number of errors. We show how the instanton method of physics allows one to solve the problem of BER analysis in the weak noise range by recasting it as a computationally tractable minimization problem.

Polaron dynamics with a multitude of Davydov D2 trial states

We propose an extension to the Davydov D2 Ansatz in the dynamics study of the Holstein molecular crystal model with diagonal and off-diagonal exciton-phonon coupling using the Dirac-Frenkel time-dependent variational principle. The new trial state by the name of the multi-D2 Ansatz is a linear combination of Davydov D2 trial states, and its validity is carefully examined by quantifying how faithfully it follows the Schrödinger equation. Considerable improvements in accuracy have been demonstrated in comparison with the usual Davydov trial states, i.e., the single D1 and D2 Ansätze. With an increase in the number of the Davydov D2 trial states in the multi-D2 Ansatz, deviation from the exact Schrödinger dynamics is gradually diminished, leading to a numerically exact solution to the Schrödinger equation.

Belief propagation and loop series on planar graphs

We discuss a generic model of Bayesian inference with binary variables defined on edges of a planar graph. The Loop Calculus approach of Chertkov and Chernyak (2006 Phys. Rev. E 73 065102(R) [cond-mat/0601487]; 2006 J. Stat. Mech. P06009 [cond-mat/0603189]) is used to evaluate the resulting series expansion for the partition function. We show that, for planar graphs, truncating the series at single-connected loops reduces, via a map reminiscent of the Fisher transformation (Fisher 1961 Phys. Rev. 124 1664), to evaluating the partition function of the dimer-matching model on an auxiliary planar graph. Thus, the truncated series can be easily re-summed, using the Pfaffian formula of Kasteleyn (1961 Physics 27 1209). This allows us to identify a big class of computationally tractable planar models reducible to a dimer model via the Belief Propagation (gauge) transformation. The Pfaffian representation can also be extended to the full Loop Series, in which case the expansion becomes a sum of Pfaffian contributions, each associated with dimer matchings on an extension to a subgraph of the original graph. Algorithmic consequences of the Pfaffian representation, as well as relations to quantum and non-planar models, are discussed.

Transition times in the low-noise limit of stochastic dynamics

We study the transition time distribution for a particle moving between two wells of a multidimensional potential in the low-noise limit of overdamped Langevin dynamics. Possible transition paths are restricted to a thin tube surrounding the most probable trajectory. We demonstrate that finding the transition time distribution reduces to a one-dimensional problem. The resulting transition time distribution has a universal and compact form. We suggest that transition barriers can be estimated from a single-temperature experiment if both the life times and the transition times are measured.