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We propose a trajectory-based quasi-classical method for approximating dynamics in condensed phase systems. Building upon the previously developed optimized mean trajectory approximation that has been used to compute linear and nonlinear spectra, we borrow some ideas from filtering trajectory methods to obtain a novel semiclassical method for the dynamical propagation of density matrices. This new approximation is tested rigorously against standard multistate electronic models, spin-boson models, and models of the Fenna-Matthews-Olson complex. For dissipative systems, the current method is significantly better or as good as many other semiclassical methods available, especially at low temperatures and for off-diagonal density matrix elements, whereas for scattering models, the current method bears similar limitations as mean-field propagation schemes. All results are tested against the numerically exact hierarchical equations of motion method. The new method shows excellent agreement across various parameter regimes with numerically exact results, highlighting the robustness and accuracy of our approach., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The third-order response lies at the heart of simulating and interpreting nonlinear spectroscopies ranging from two-dimensional infrared (2D-IR) to 2D electronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra time and frequency dimensions in these spectroscopic techniques provide access to rich information on the electronic and vibrational states present, the coupling between them, and the resulting rates at which they exchange energy that are obscured in linear spectroscopy, particularly for condensed phase systems that usually contain many overlapping features. While the exact quantum expression for the third-order response is well established, it is incompatible with the methods that are practical for calculating the atomistic dynamics of large condensed phase systems. These methods, which include both classical mechanics and quantum dynamics methods that retain quantum statistical properties while obeying the symmetries of classical dynamics, such as LSC-IVR, centroid molecular dynamics, and Ring Polymer Molecular Dynamics (RPMD), naturally provide short-time approximations to the multi-time symmetrized Kubo transformed correlation function. Here, we show how the third-order response can be formulated in terms of equilibrium symmetrized Kubo transformed correlation functions. We demonstrate the utility and accuracy of our approach by showing how it can be used to obtain the third-order response of a series of model systems using both classical dynamics and RPMD. In particular, we show that this approach captures features such as anharmonically induced vertical splittings and peak shifts while providing a physically transparent framework for understanding multidimensional spectroscopies. [ABSTRACT FROM AUTHOR]

The two-step quench process of surface-directed spinodal decomposition is numerically investigated by coupling the Flory–Huggins–de Gennes equation with the Cahn–Hilliard–Cook equation. The phase dynamics and formation mechanisms of the wetting layer in two-step surface-directed spinodal decomposition have been concerned in detail. The results demonstrate that a parallel strip structure forms near the wetting layer and propagates into the bulk, when the first quench depth is very shallow and the bulk does not undergo phase separation, and the second quench depths are various points with deeper quench depths. In this case, the wetting layer turns to be unchangeable at the intermediate and later stages of the second quench process, compared to the growth with a time exponent 1/2 during the first quench process. When the first quench depth is deeper and phase separation occurs in the bulk during the first quench process, it is found that a deeper second quench depth can stimulate a more obvious secondary domain structure, and the formation mechanism of the wetting layer changes from logarithmic growth law to Lifshitz–Slyozov growth law. [ABSTRACT FROM AUTHOR]

We investigate the quantum-phase dynamics of a dissipative molecular system interacting with a single-mode amplitude-squeezed field (with a sub-Poissonian photon-number distribution) using the Monte Carlo wave-function method. As quantum dissipation, we consider molecular coherent (phase) and population relaxations, which are caused by nuclear vibration, and cavity relaxation (the dissipation of an internal single mode to outer mode). In this study, we elucidate the effects of these dissipations on the unique quantum dynamical behaviors of this coupled system, e.g., collapse-revival behavior of Rabi oscillations, using the quasiprobability (Q function) distribution of a single-mode field and the off-diagonal molecular density matrix. It is found that although the amplitude-squeezed field exhibits a distinct revival with larger amplitudes of molecular population in the presence of the molecular phase and population relaxations as compared to the coherent field, a very slight cavity relaxation suppresses the revival of molecular population and the increase in the magnitude of off-diagonal molecular density matrices during the quiescent region in the amplitude-squeezed field case more significantly than in the coherent field case. These features are shown to be closely related to the difference in the dynamics of Q function distributions between amplitude-squeezed and coherent fields. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O–H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra. [ABSTRACT FROM AUTHOR]

We investigate the intermolecular-interaction (dipole-dipole interaction) effects on the quantum dynamics of dimer density matrices and photon-phase distributions using several dimer models with different intermolecular distances in the presence of a two-mode squeezed vacuum field. In this photon field, each mode is initially correlated and the reduced one-mode photon distribution is equivalent with that of a thermal field. For comparison, we perform parallel studies, in which the initial fields are two types of noncorrelated two-mode fields, i.e., a two-mode coherent field and a two-mode thermal field. It is found that although the two-mode squeezed vacuum field causes the random oscillations of dimer populations in the noninteracting dimer, the periodic oscillations like the collapse-revival behavior emerge as the intermolecular distance decreases (the intermolecular interaction increases). Similar and dissimilar features among quantum dynamics caused by these three types of fields are investigated by analyzing the dynamical behavior of two-mode PeggBarnett photon-phase distributions and off-diagonal dimer density matrices, which indicate the coherency between dimer states. In addition to the quantum statistical properties of initial photon field, the change in the degree of contribution between one- and two-photon processes caused by the intermolecular interaction is found to be important to determine these features. [ABSTRACT FROM AUTHOR]

It is well-known that the interaction among atoms/molecules and quantized electromagnetic fields with a small number of photons provides a peculiar quantum nature, i.e., collapses and revivals in the Rabi oscillations. In this study, we investigate the intermolecular interaction (dipole-dipole interaction) effect on the collapse-revival behavior using several dimer models (composed of two kinds of two-state monomers with slightly different excitation energies) with different intermolecular distances in the presence of a two-mode squeezed coherent field, in which each mode is initially correlated. It is found that although the collapse-revival behavior is fairly overlapped and indistinct in the case of a noninteracting dimer under the present two-mode squeezed coherent field, the decrease in the intermolecular distance (the increase in the intermolecular interaction) resurrects relatively distinct collapse-revival behavior with longer collapse and revival times. By analyzing the quantum behavior from the viewpoint of the dynamics of two-mode Pegg-Barnett photon-phase distributions and off-diagonal dimer density matrices, this feature is found to closely relate to a significant change in the degree of contribution between one- and two-photon processes caused by the variation in the intermolecular interaction. [ABSTRACT FROM AUTHOR]

Picosecond transient grating experiments in sodium and iodine vapors, involving the 3S→3P and X→B transitions, respectively, are discussed in detail. Population gratings in sodium demonstrate that the technique can be used to measure velocity distributions in the gas phase. It is shown that the time dependent transient grating signal is related to the Fourier transform of the velocity distribution. Similar experiments on iodine illustrate the effect of state changing collisions on the grating signal. Theoretical calculations for a model in which the change of state is caused by a single collision are given. Close agreement with the data is observed for the situation in which the collision takes the initial velocity into a random velocity distribution. From this model a collision cross section is determined. The results demonstrate that information on collision dynamics can be obtained from grating experiments. In addition, the sodium experiments are used to illustrate a new type of time domain high resolution spectroscopy. When the grating excitation pulses have perpendicular polarizations, a polarization grating, rather than the usual population grating, is formed. Diffraction from the sodium polarization grating shows larger time dependent oscillations in the diffraction efficiency. These oscillations yield the ground state and excited state hyperfine frequencies (1.77 GHz and 189 MHz, respectively). A detailed theoretical description of the origin of the oscillations is presented. The results suggest that polarization grating spectroscopy can have applications in other areas, such as molecular rotational dynamics. [ABSTRACT FROM AUTHOR]

The two-step quench process of surface-directed spinodal decomposition is numerically investigated by coupling the Flory-Huggins-de Gennes equation with the Cahn-Hilliard-Cook equation. The phase dynamics and formation mechanisms of the wetting layer in two-step surface-directed spinodal decomposition have been concerned in detail. The results demonstrate that a parallel strip structure forms near the wetting layer and propagates into the bulk, when the first quench depth is very shallow and the bulk does not undergo phase separation, and the second quench depths are various points with deeper quench depths. In this case, the wetting layer turns to be unchangeable at the intermediate and later stages of the second quench process, compared to the growth with a time exponent 1/2 during the first quench process. When the first quench depth is deeper and phase separation occurs in the bulk during the first quench process, it is found that a deeper second quench depth can stimulate a more obvious secondary domain structure, and the formation mechanism of the wetting layer changes from logarithmic growth law to Lifshitz-Slyozov growth law.

Low-energy and high-energy collision induced dissociation techniques are used to study the dissociation behavior of the gaseous Pt(CN)[sub 6][sup 2-] and Pt(CN)[sub 4][sup 2-] dianion complexes in order to probe the smallest stable dianion complex. Loss of neutral molecules from Pt(CN)[sub 6][sup 2-] occurs resulting in Pt(CN)[sub 5][sup 2-] and Pt(CN)[sub 4][sup 2-], but no indication of the existence of Pt(CN)[sub 3][sup 2-] was found. This indicates that the lifetime of Pt(CN)[sub 3][sup 2-] is less than 4 μs (the flight time from the collision region to the detector). In contrast, all monoanion platinum-cyanide complexes were observed, i.e., Pt(CN)[sub n][sup -] (n=1-6). The kinetic energy released in processes where monoanions are formed is much lower than the barrier height for the reverse reaction (>1.5 eV), which indicates that electron detachment is involved, e.g., Pt(CN)[sub 3][sup -] and CN[sup -] are not formed in the same dynamical process from Pt(CN)[sub 4][sup 2-], or that the dynamics of the dissociation process is slow. For comparison, the Ru(bipy)[sub 3][sup 2+*]→[Ru(bipy)[sub 2]-H][sup +]+bipyH[sup +] reaction is associated with a kinetic-energy release of ∼0.3 eV (bipy=2,2[sup ′]-bipyridine). © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

This study presents the detailed characterization of a magnetron-based Ar–N2 plasma discharge used to sputter a liquid Ga target for the deposition of gallium nitride (GaN) thin films. By utilizing in situ diagnostic techniques including optical emission spectroscopy and microwave interferometry, we determine different temperatures (rotational and vibrational of N2 molecules, and electronic excitation of Ar atoms) and electron density, respectively. Beyond providing insights into fundamental plasma physics, our research establishes a significant correlation between gas-phase dynamics, particularly those of gallium atoms (flux and average energy at the substrate) and deposited GaN thin film properties (growth rate and crystalline fraction). These findings underscore the role of plasma conditions in enhancing thin film quality, highlighting the importance of plasma characterization in understanding and optimizing GaN thin film growth processes. [ABSTRACT FROM AUTHOR]

The Structure and TOpology Replica Molecular Mechanics (STORMM) code is a next-generation molecular simulation engine and associated libraries optimized for performance on fast, vectorized central processor units and graphics processing units (GPUs) with independent memory and tens of thousands of threads. STORMM is built to run thousands of independent molecular mechanical calculations on a single GPU with novel implementations that tune numerical precision, mathematical operations, and scarce on-chip memory resources to optimize throughput. The libraries are built around accessible classes with detailed documentation, supporting fine-grained parallelism and algorithm development as well as copying or swapping groups of systems on and off of the GPU. A primary intention of the STORMM libraries is to provide developers of atomic simulation methods with access to a high-performance molecular mechanics engine with extensive facilities to prototype and develop bespoke tools aimed toward drug discovery applications. In its present state, STORMM delivers molecular dynamics simulations of small molecules and small proteins in implicit solvent with tens to hundreds of times the throughput of conventional codes. The engineering paradigm transforms two of the most memory bandwidth-intensive aspects of condensed-phase dynamics, particle–mesh mapping, and valence interactions, into compute-bound problems for several times the scalability of existing programs. Numerical methods for compressing and streamlining the information present in stored coordinates and lookup tables are also presented, delivering improved accuracy over methods implemented in other molecular dynamics engines. The open-source code is released under the MIT license. [ABSTRACT FROM AUTHOR]

Two-dimensional infrared (2D-IR) spectroscopy is used to measure the spectral dynamics of the metal carbonyl complex cyclopentadienyl manganese tricarbonyl (CMT) in a series of linear alkyl nitriles. 2D-IR spectroscopy provides direct readout of solvation dynamics through spectral diffusion, probing the decay of frequency correlation induced by fluctuations of the solvent environment. 2D-IR simultaneously monitors intramolecular vibrational energy redistribution (IVR) among excited vibrations, which can also be influenced by the solvent through the spectral density rather than the dynamical friction underlying solvation. Here, we report that the CMT vibrational probe reveals solvent dependences in both the spectral diffusion and the IVR time scales, where each slows with increased alkyl chain length. In order to assess the degree to which solute–solvent interactions can be correlated with bulk solvent properties, we compared our results with low-frequency dynamics obtained from optical Kerr effect (OKE) spectroscopy—performed by others—on the same nitrile solvent series. We find excellent correlation between our spectral diffusion results and the orientational dynamics time scales from OKE. We also find a correlation between our IVR time scales and the amplitudes of the low-frequency spectral densities evaluated at the 90-cm−1 energy difference, corresponding to the gap between the two strong vibrational modes of the carbonyl probe. 2D-IR and OKE provide complementary perspectives on condensed phase dynamics, and these findings provide experimental evidence that at least at the level of dynamical correlations, some aspects of a solute vibrational dynamics can be inferred from properties of the solvent. [ABSTRACT FROM AUTHOR]

Condensed phase electron transfer problems are often simplified by making the Condon approximation: the approximation that the coupling connecting two charge-transfer diabatic states is a constant. Unfortunately, the Condon approximation does not predict the existence of conical intersections, which are ubiquitous in both gas-phase and condensed-phase photochemical dynamics. In this paper, we develop a formalism to treat condensed-phase dynamics beyond the Condon approximation. We show that even for an extremely simple test system, hexaaquairon(ii)/hexaaquairon(iii) self-exchange in water, the electronic coupling is expected to fluctuate rapidly and non-Condon effects must be considered to obtain quantitatively accurate ultrafast nonequilibrium dynamics. As diabatic couplings are expected to fluctuate substantially in many condensed-phase electron transfer systems, non-Condon effects may be essential to quantitatively capture accurate short-time dynamics. [ABSTRACT FROM AUTHOR]

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabatic transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules. [ABSTRACT FROM AUTHOR]

Bimolecular reactions in the gas phase exhibit rich and varied dynamical behaviour, but whether a profound knowledge of the mechanisms of isolated reactive collisions can usefully inform our understanding of reactions in liquid solutions remains an open question. The fluctuating environment in a liquid may significantly alter the motions of the reacting particles and the flow of energy into the reaction products after a transition state has been crossed. Recent experimental and computational studies of exothermic reactions of CN radicals with organic molecules indicate that many features of the gas-phase dynamics are retained in solution. However, observed differences may also provide information on the ways in which a solvent modifies fundamental chemical mechanisms. This perspective examines progress in the use of time-resolved infra-red spectroscopy to study reaction dynamics in liquids, discusses how existing theories can guide the interpretation of experimental data, and suggests future challenges for this field of research. [ABSTRACT FROM AUTHOR]

The twisting motion of trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (4-DASPI) in the excited state was investigated in solutions and various polymers in order to understand dependence of molecular rotor dynamics on viscoelasticity. It was observed that the internal motion of electronically excited 4-DASPI correlates strongly with dynamic viscosity and elastic modulus. Our results also showed that condensed phase dynamics of 4-DASPI are governed by the explicit mode coupling between the rotamerizing coordinate and mechanical properties of viscoelastic media. [ABSTRACT FROM AUTHOR]

The isotropic phase dynamics of a system of 4-n-hexyl-4′-cyano-biphenyl (6CB) molecules has been studied by molecular dynamics computer simulations. We have explored the range of 275–330 K keeping the system isotropic, although supercooled under its nematic transition temperature. The weak rototranslational coupling allowed us to separately evaluate translational (TDOF) and orientational degrees of freedom (ODOF). Evidences of subdiffusive dynamics, more apparent at the lowest temperatures, are found in translational and orientational dynamics. Mean square displacement as well as self-intermediate center of mass and rotational scattering functions show a plateau, also visible in the orientational correlation function. According to the mode coupling theory (MCT), this plateau is the signature of the β-relaxation regime. Three-time intermediate scattering functions reveal that the plateau is related to a homogeneous dynamics, more extended in time for the orientational degrees of freedom (up to 1 ns). The time-temperature superposition principle and the factorization property predicted by the idealized version of MCT hold, again for both kinds of dynamics. The temperature dependence of diffusion coefficient and orientational relaxation time is well described by a power law. Critical temperatures Tc are 244±6 and 258±6 K, respectively, the latter is some 10 K below the corresponding experimental values. The different values of Tc we obtained indicate that ODOF freezes earlier than TDOF. This appears due to the strongly anisotropic environment that surrounds a 6CB molecule, even in the isotropic phase. The lifetime of these “cages,” estimated by time dependent conditional probability functions, is strongly temperature dependent, ranging from some hundreds of picoseconds at 320 K to a few nanoseconds at 275 K. [ABSTRACT FROM AUTHOR]

A numerically exact quantum mechanical approach is proposed to evaluate thermal rate constants for systems in a model condensed phase environment. Employing the reactive flux correlation function formalism, the approach efficiently combines the multilayer multiconfiguration time-dependent Hartree theory with an importance sampling scheme for thermal distribution of the initial states. The performance of the method is illustrated by applications to two models of condensed phase dynamics: the donor-acceptor electron transfer model also known as the spin-boson model and a model for proton transfer reactions in the condensed phase. [ABSTRACT FROM AUTHOR]

A detailed three-dimensional time-dependent quantum dynamical study of the He+H2+(v=0–3,j=0)→HeH++H reaction is reported for different vibrational v states of H2+ in its ground rotational (j=0) state over a range of translational Etrans energies on an accurate ab initio potential energy surface published by Palmieri et al. Plots of reaction probability as a function of total energy E reveal a large number of oscillations indicating the presence of a number of reactive scattering resonances. When averaged over total angular momentum J, some of the oscillations survive, indicating that they may be amenable to experimental observation. A comparison of our present results with our earlier results on the McLaughlin–Thompson–Joseph–Sathyamurthy surface and the experimental results from different research groups reveal a good deal of agreement as well as some discrepancies between theory and experiment at the level of state-selected gas phase dynamics. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A novel four-pulse photon-echo technique for exploring condensed phase dynamics at different parts of the excited-state potential energy surface is presented. In contrast to traditional three-pulse photon-echo signals, the introduction of a fourth pump pulse allows the use of photon-echo techniques to probe excited-state phenomena. Here, a “proof of principle” experiment is presented where the excited-state solvent dynamics of the coumarin 153 chromophore dissolved in methanol is explored. The fluctuations of the stimulated emission transition is probed, in contrast to the ground-state absorption transition explored in traditional echo measurements. Distinctly different excited-state dynamics, in contrast to ground-state signals, is observed and discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper, we present a new method for simulating the evolution of the phase space distribution function describing a system coupled to a Markovian thermal bath. The approach is based on the propagation of ensembles of trajectories. Instead of incorporating environmental perturbations as stochastic forces, however, the present method includes these effects by additional deterministic interactions between the ensemble members. The general formalism is developed and tested on model systems describing one-dimensional diffusion, relaxation of a coherently excited harmonic oscillator coupled to a thermal bath, and activated barrier crossing in a bistable potential. Excellent agreement with exact results or approximate theories is obtained in all cases. The method provides an entirely deterministic trajectory-based approach to the solution of condensed phase dynamics and chemical reactions. [ABSTRACT FROM AUTHOR]

Compares the coherent higher order Raman excitation (CHORES) and coherent anti-stokes Raman scattering (CARS) for liquid phase dynamics. Similarity of CORES and CARS in terms of phase matching conditions; Effects of overtone coherence on time-resolved (TR)-CHORES; Behavior of TR-SCARS in time dependence.

Investigates the ultrafast multi-state nuclear dynamics in triatomic cluster. Determination of femtosecond intramolecular, cluster and condensed phase dynamics on timescale of nuclear motion; Simulation of negative ion-to neutral-to positive ion (NENEPO)-zero kinetic energy signal; Analysis of vibrational coherence effects in NENEPO signals.

Presents kinetics measurements and time-resolved spectra that provide insight into the condensed-phase dynamics of cis-hexatriene in cyclohexane in the ground and excited states. Vibrational cooling results in trapping of a small amount that relaxes on a much longer time scale as the barrier to isomerization.

Alchemical free energy calculations via molecular dynamics have been applied to obtain thermodynamic properties related to solid–liquid equilibrium conditions, such as melting points. In recent years, the pseudo-supercritical path (PSCP) method has proved to be an important approach to melting point prediction due to its flexibility and applicability. In the present work, we propose improvements to the PSCP alchemical cycle to make it more compact and efficient through a concerted evaluation of different potential energies. The multistate Bennett acceptance ratio (MBAR) estimator was applied at all stages of the new cycle to provide greater accuracy and uniformity, which is essential concerning uncertainty calculations. In particular, for the multistate expansion stage from solid to liquid, we employed the MBAR estimator with a reduced energy function that allows affine transformations of coordinates. Free energy and mean derivative profiles were calculated at different cycle stages for argon, triazole, propenal, and the ionic liquid 1-ethyl-3-methyl-imidazolium hexafluorophosphate. Comparisons showed a better performance of the proposed method than the original PSCP cycle for systems with higher complexity, especially the ionic liquid. A detailed study of the expansion stage revealed that remapping the centers of mass of the molecules or ions is preferable to remapping the coordinates of each atom, yielding better overlap between adjacent states and improving the accuracy of the methodology. [ABSTRACT FROM AUTHOR]

This paper reports the release of PathSum, a new software suite of state-of-the-art path integral methods for studying the dynamics of single or extended systems coupled to harmonic environments. The package includes two modules, suitable for system–bath problems and extended systems comprising many coupled system–bath units, and is offered in C++ and Fortran implementations. The system–bath module offers the recently developed small matrix path integral (SMatPI) and the well-established iterative quasi-adiabatic propagator path integral (i-QuAPI) method for iteration of the reduced density matrix of the system. In the SMatPI module, the dynamics within the entanglement interval can be computed using QuAPI, the blip sum, time evolving matrix product operators, or the quantum–classical path integral method. These methods have distinct convergence characteristics and their combination allows a user to access a variety of regimes. The extended system module provides the user with two algorithms of the modular path integral method, applicable to quantum spin chains or excitonic molecular aggregates. An overview of the methods and code structure is provided, along with guidance on method selection and representative examples. [ABSTRACT FROM AUTHOR]

Molecular dynamics (MD) simulations of gas-phase chemical reactions are typically carried out on a small number of molecules near thermal equilibrium by means of various thermostatting algorithms. Correct equipartitioning of kinetic energy among translations, rotations, and vibrations of the simulated reactants is critical for many processes occurring in the gas phase. As thermalizing collisions are infrequent in gas-phase simulations, the thermostat has to efficiently reach equipartitioning in the system during equilibration and maintain it throughout the actual simulation. Furthermore, in non-equilibrium simulations where heat is released locally, the action of the thermostat should not lead to unphysical changes in the overall dynamics of the system. Here, we explore issues related to both obtaining and maintaining thermal equilibrium in MD simulations of an exemplary ion–molecule dimerization reaction. We first compare the efficiency of global (Nosé–Hoover and Canonical Sampling through Velocity Rescaling) and local (Langevin) thermostats for equilibrating a system of flexible compounds and find that of these three only the Langevin thermostat achieves equipartition in a reasonable simulation time. We then study the effect of the unphysical removal of latent heat released during simulations involving multiple dimerization events. As the Langevin thermostat does not produce the correct dynamics in the free molecular regime, we only consider the commonly used Nosé–Hoover thermostat, which is shown to effectively cool down the reactants, leading to an overestimation of the dimerization rate. Our findings underscore the importance of thermostatting for the proper thermal initialization of gas-phase systems and the consequences of global thermostatting in non-equilibrium simulations. [ABSTRACT FROM AUTHOR]

Some topological features of multisite Hamiltonians consisting of harmonic potential surfaces with constant site-to-site couplings are discussed. Even in the absence of Duschinsky rotation, such a Hamiltonian assumes the system-bath form only if severe constraints exist. The simplest case of a common bath that couples to all sites is realized when the potential minima are collinear. The bath reorganization energy increases quadratically with site distance in this case. Another frequently encountered situation involves exciton-vibration coupling in molecular aggregates, where the intramolecular normal modes of the monomers give rise to local harmonic potentials. In this case, the reorganization energy accompanying excitation transfer is independent of site-to-site separation, thus this situation cannot be described by the usual system-bath Hamiltonian. A vector system-bath representation is introduced, which brings the exciton-vibration Hamiltonian in system-bath form. In this, the system vectors specify the locations of the potential minima, which in the case of identical monomers lie on the vertices of a regular polyhedron. By properly choosing the system vectors, it is possible to couple each bath to one or more sites and to specify the desired initial density. With a collinear choice of system vectors, the coupling reverts to the simple form of a common bath. The compact form of the vector system-bath coupling generalizes the dissipative tight-binding model to account for local, correlated, and common baths. The influence functional for the vector system-bath Hamiltonian is obtained in a compact and simple form. [ABSTRACT FROM AUTHOR]

We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the nuclei on the active adiabatic potential-energy surface, such as in FSSH. However, unlike in FSSH, transitions between active surfaces are deterministic and occur when the electronic mapping variables evolve between specified regions of the electronic phase space. This guarantees internal consistency between the active surface and the electronic degrees of freedom throughout the dynamics. MASH is rigorously derivable from exact quantum mechanics as a limit of the quantum–classical Liouville equation (QCLE), leading to a unique prescription for momentum rescaling and frustrated hops. Hence, a quantum-jump procedure can, in principle, be used to systematically converge the accuracy of the results to that of the QCLE. This jump procedure also provides a rigorous framework for deriving approximate decoherence corrections similar to those proposed for FSSH. We apply MASH to simulate the nonadiabatic dynamics in various model systems and show that it consistently produces more accurate results than FSSH at a comparable computational cost. [ABSTRACT FROM AUTHOR]

The nonadiabatic phenomena, which are characterized by a strong coupling between electronic and nuclear motions, are ubiquitous. The nonadiabatic effect of the studied system can be significantly affected by the surrounding environment, such as solvents, in which such nonadiabatic process takes place. It is essential to develop the theoretical models to simulate these processes while accurately modeling the solvent environment. The time-dependent density functional theory (TDDFT) is currently the most efficient approach to describe the electronic structures and dynamics of complex systems, while the polarizable continuum model (PCM) represents one of the most successful examples among continuum solvation models. Here, we formulate the first-order derivative couplings (DCs) between the ground and excited states as well as between two excited states by utilizing time-independent equation of motion formalism within the framework of both linear response and spin flip formulations of TDDFT/CPCM (the conductor-like PCM), and implement the analytical DCs into the Q-CHEM electronic structure software package. The analytic implementation is validated by the comparison of the analytical and finite-difference results, and reproducing geometric phase effect in the protonated formaldimine test case. Taking 4-(N,N-dimethylamino)benzonitrile and uracil in the gas phase and solution as an example, we demonstrate that the solvent effect is essential not only for the excitation energies of the low-lying excited-states but also for the DCs between these states. Finally, we calculate the internal conversion rate of benzophenone in a solvent with DC being used. The current implementation of analytical DCs together with the existing analytical gradient and Hessian of TDDFT/PCM excited states allows one to study the nonadiabatic effects of relatively large systems in solutions with low computational cost. [ABSTRACT FROM AUTHOR]

The formalism of the generalized quantum master equation (GQME) is an effective tool to simultaneously increase the accuracy and the efficiency of quasiclassical trajectory methods in the simulation of nonadiabatic quantum dynamics. The GQME expresses correlation functions in terms of a non-Markovian equation of motion, involving memory kernels that are typically fast-decaying and can therefore be computed by short-time quasiclassical trajectories. In this paper, we study the approximate solution of the GQME, obtained by calculating the kernels with two methods: Ehrenfest mean-field theory and spin-mapping. We test the approaches on a range of spin–boson models with increasing energy bias between the two electronic levels and place a particular focus on the long-time limits of the populations. We find that the accuracy of the predictions of the GQME depends strongly on the specific technique used to calculate the kernels. In particular, spin-mapping outperforms Ehrenfest for all the systems studied. The problem of unphysical negative electronic populations affecting spin-mapping is resolved by coupling the method with the master equation. Conversely, Ehrenfest in conjunction with the GQME can predict negative populations, despite the fact that the populations calculated from direct dynamics are positive definite. [ABSTRACT FROM AUTHOR]

We investigate a spin-boson inspired model of electron transfer, where the diabatic coupling is given by a position-dependent phase, eiWx. We consider both equilibrium and nonequilibrium initial conditions. We show that, for this model, all equilibrium results are completely invariant to the sign of W (to infinite order). However, the nonequilibrium results do depend on the sign of W, suggesting that photo-induced electron transfer dynamics with spin–orbit coupling can exhibit electronic spin polarization (at least for some time). [ABSTRACT FROM AUTHOR]

The collective vibrational excitations of two different crystalline monolayer phases of ethane (C2H6) adsorbed on the graphite (0001) surface have been investigated theoretically and experimentally. The monolayer phases studied are the commensurate 7/8 ×4 structure in which the ethane molecules lie on their side in a herringbone arrangement and the commensurate 7/8 × 7/8 structure in which the molecules stand on-end with the C–C bond perpendicular to the surface. Semiempirical atom–atom potentials have been used to model the intermolecular and molecule–substrate interactions in calculations of the monolayer structure and lattice dynamics. The observed inelastic neutron scattering spectra below 4.1 THz are compared with calculated one-phonon incoherent cross sections. The calculated cross sections qualitatively reproduce the rather different spectra of the two phases and enable an identification of the observed vibrational modes. Moreover, they suggest that an important feature of the herringbone phase dynamics is a coupling of the lowest-frequency librational mode to the vibratory mode perpendicular to the surface. Calculations of the phonon dispersion relations, the phonon density of states, and the phonon contribution to heat capacities of the two monolayer phases are also presented and discussed. [ABSTRACT FROM AUTHOR]

We report an unusual pressure dependence of the gas phase dynamics of alkali diatomics in 1Π excited states in their interactions with certain collision partners. This behavior consists of a change in the relative rates of the ΔJ=+1 and ΔJ=-1 collision-induced transitions, which results in a dominance of rotational excitation at high pressures. This effect occurs only for the e Λ-doublet component of the excited 1Π state. Also observed is a change in the polarization of the parent line such that the polarization ratio increases with increasing pressure. The dependence of this behavior on intermolecular potential, reduced duration of collision, rotational state, and temperature lead us to propose that a long-lived complex or orbiting resonance is responsible for the effects observed. This species appears to be formed during the lifetime of the excited state of the diatomic. Knowledge of the molecule-fixed geometry of the Λ doublets allows us to propose a structure for the long-lived species and to speculate that the observed characteristic rotational excitation results from specific vibrational and rotational predissociation processes within the complex. [ABSTRACT FROM AUTHOR]

Nonadiabatic molecular dynamics occur in a wide range of chemical reactions and femtochemistry experiments involving electronically excited states. These dynamics are hard to treat numerically as the system's complexity increases, and it is thus desirable to have accurate yet affordable methods for their simulation. Here, we introduce a linearized semiclassical method, the generalized discrete truncated Wigner approximation (GDTWA), which is well-established in the context of quantum spin lattice systems, into the arena of chemical nonadiabatic systems. In contrast to traditional continuous mapping approaches, e.g., the Meyer–Miller–Stock–Thoss and the spin mappings, GDTWA samples the electron degrees of freedom in a discrete phase space and thus forbids an unphysical unbounded growth of electronic state populations. The discrete sampling also accounts for an effective reduced but non-vanishing zero-point energy without an explicit parameter, which makes it possible to treat the identity operator and other operators on an equal footing. As numerical benchmarks on two linear vibronic coupling models and Tully's models show, GDTWA has a satisfactory accuracy in a wide parameter regime, independent of whether the dynamics is dominated by relaxation or by coherent interactions. Our results suggest that the method can be very adequate to treat challenging nonadiabatic dynamics problems in chemistry and related fields. [ABSTRACT FROM AUTHOR]

A theoretical and experimental study of the gas phase and liquid acetic acid based on resonant inelastic x-ray scattering (RIXS) spectroscopy is presented. We combine and compare different levels of theory for an isolated molecule for a comprehensive analysis, including electronic and vibrational degrees of freedom. The excitation energy scan over the oxygen K-edge absorption reveals nuclear dynamic effects in the core-excited and final electronic states. The theoretical simulations for the monomer and two different forms of the dimer are compared against high-resolution experimental data for pure liquid acetic acid. We show that the theoretical model based on a dimer describes the hydrogen bond formation in the liquid phase well and that this bond formation sufficiently alters the RIXS spectra, allowing us to trace these effects directly from the experiment. Multimode vibrational dynamics is accounted for in our simulations by using a hybrid time-dependent stationary approach for the quantum nuclear wave packet simulations, showing the important role it plays in RIXS. [ABSTRACT FROM AUTHOR]

Electron paramagnetic resonance (EPR) spectroscopy is used to address the remarkable persistence of the native Arrhenius dependence of the 2-aminopropanol substrate radical rearrangement reaction in B12-dependent ethanolamine ammonia-lyase (EAL) from Salmonella typhimurium from physiological to cryogenic (220 K) temperatures. Two-component TEMPOL spin probe mobility in the presence of 10 mM (0.08% v/v) 2-aminopropanol over 200–265 K demonstrates characteristic concentric aqueous-cosolvent mesodomain and protein-associated domain (PAD, hydration layer) solvent phases around EAL in the frozen solution. The mesodomain formed by the relatively small amount of 2-aminopropanol is highly confined, as shown by an elevated temperature for the order–disorder transition (ODT) in the PAD (230–235 K) and large activation energy for TEMPOL rotation. Addition of 2% v/v dimethylsulfoxide expands the mesodomain, partially relieves PAD confinement, and leads to an ODT at 205–210 K. The ODT is also manifested as a deviation of the temperature-dependence of the EPR amplitude of cob(II)alamin and the substrate radical, bound in the enzyme active site, from Curie law behavior. This is attributed to an increase in sample dielectric permittivity above the ODT at the microwave frequency of 9.5 GHz. The relatively high frequency dielectric response indicates an origin in coupled protein surface group–water fluctuations of the Johari–Goldstein β type that span spatial scales of ∼0.1–10 Å on temporal scales of 10−10–10−7 s. The orthogonal EPR spin probe rotational mobility and solvent dielectric measurements characterize features of EAL protein–solvent dynamical coupling and reveal that excess substrate acts as a fluidizing cryosolvent to enable native enzyme reactivity at cryogenic temperatures. [ABSTRACT FROM AUTHOR]

Infrared spectroscopic studies of weakly bound clusters isolated in solid parahydrogen (pH2) that exhibit large-amplitude tunneling motions are needed to probe how quantum solvation perturbs these types of coherent dynamics. We report high resolution Fourier transform infrared absorption spectra of (HCl)2, HCl–DCl, and (DCl)2 isolated in solid pH2 in the 2.4–4.8 K temperature range. The (HCl)2 spectra show a remarkable amount of fine structures that can be rigorously assigned to vibration–rotation–tunneling transitions of (HCl)2 trapped in double substitution sites in the pH2 matrix where end-over-end rotation of the cluster is quenched. The spectra are assigned using a combination of isotopically (H/D and 35Cl/37Cl) enriched samples, polarized IR absorption measurements, and four-line combination differences. The interchange-tunneling (IT) splitting in the ground vibrational state for in-plane and out-of-plane H35Cl–H37Cl dimers is 6.026(1) and 6.950(1) cm−1, respectively, which are factors of 2.565 and 2.224 smaller than in the gas phase dimer. In contrast, the (DCl)2 results show larger perturbations where the ground vibrational state IT splitting in D35Cl–D37Cl is 1.141(1) cm−1, which is a factor of 5.223 smaller than in the gas phase, and the tunneling motion is quenched in excited intramolecular vibrational states. The results are compared to similar measurements on (HCl)2 made in liquid helium nanodroplets to illustrate the similarities and differences in how both these quantum solvents interact with large amplitude tunneling motions of an embedded chromophore. [ABSTRACT FROM AUTHOR]

The p53 transcription factor is a key mediator in cellular responses to various stress signals including DNA repair, cell cycle arrest, and apoptosis. In this work, we employ landscape and flux theory to investigate underlying mechanisms of p53-regulated cell fate decisions. Based on a p53 regulatory network, we quantified the potential landscape and probabilistic flux for the p53 system. The landscape topography unifies and quantifies three cell fate states, including the limit cycle oscillations (representing cell cycle arrest), high p53 state (characterizing apoptosis), and low p53 state (characterizing the normal proliferative state). Landscape and flux results provide a quantitative explanation for the biphasic dynamics of the p53 system. In the oscillatory phase (first phase), the landscape attracts the system into the ring valley and flux drives the system cyclically moving, leading to cell cycle arrest. In the fate decision-making phase (second phase), the ring valley shape of the landscape provides an efficient way for cells to return to the normal proliferative state once DNA damage is repaired. If the damage is unrepairable with larger flux, the system may cross the barrier between two states and switch to the apoptotic state with a high p53 level. By landscape-flux decomposition, we revealed a trade-off between stability (guaranteed by landscape) and function (driven by flux) in cellular systems. Cells need to keep a balance between appropriate speed to repair DNA damage and appropriate stability to survive. This is further supported by flux landscape analysis showing that flux may provide the dynamical origin of phase transition in a non-equilibrium system by changing landscape topography. [ABSTRACT FROM AUTHOR]

We investigate memory effects in barrier-crossing in the overdamped setting. We focus on the scenario where the hidden degrees of freedom relax on exactly the same time scale as the observable. As a prototypical model, we analyze tagged-particle diffusion in a single file confined to a bi-stable potential. We identify the signatures of memory and explain their origin. The emerging memory is a result of the projection of collective many-body eigenmodes onto the motion of a tagged-particle. We are interested in the "confining" (all background particles in front of the tagged-particle) and "pushing" (all background particles behind the tagged-particle) scenarios for which we find non-trivial and qualitatively different relaxation behaviors. Notably and somewhat unexpectedly, at a fixed particle number, we find that the higher the barrier, the stronger the memory effects are. The fact that the external potential alters the memory is important more generally and should be taken into account in applications of generalized Langevin equations. Our results can readily be tested experimentally and may be relevant for understanding transport in biological ion-channels. [ABSTRACT FROM AUTHOR]

Water is at the heart of almost all biological phenomena, without which no life that we know of would have been possible. It is a misleadingly complex liquid that exists in near coexistence with the vapor phase under ambient conditions. Confinement within a hydrophobic cavity can tip this balance enough to drive a cooperative dewetting transition. For a nanometer-scale pore, the dewetting transition leads to a stable dry state that is physically open but impermeable to ions. This phenomenon is often referred to as hydrophobic gating. Numerous transmembrane protein ion channels have now been observed to utilize hydrophobic gating in their activation and regulation. Here, we review recent theoretical, simulation, and experimental studies that together have started to establish the principles of hydrophobic gating and discuss how channels of various sizes, topologies, and biological functions can utilize these principles to control the thermodynamic properties of water within their interior pores for gating and regulation. Exciting opportunities remain in multiple areas, particularly on direct experimental detection of hydrophobic dewetting in biological channels and on understanding how the cell may control the hydrophobic gating in regulation of ion channels. [ABSTRACT FROM AUTHOR]

The characterization of an ionic liquid's properties based on structural information is a longstanding goal of computational chemistry, which has received much focus from ab initio and molecular dynamics calculations. This work examines kernel ridge regression models built from an experimental dataset of 2212 ionic liquid melting points consisting of diverse ion types. Structural descriptors, which have been shown to predict quantum mechanical properties of small neutral molecules within chemical accuracy, benefit from the addition of first-principles data related to the target property (molecular orbital energy, charge density profile, and interaction energy based on the geometry of a single ion pair) when predicting the melting point of ionic liquids. Out of the two chosen structural descriptors, ECFP4 circular fingerprints and the Coulomb matrix, the addition of molecular orbital energies and all quantum mechanical data to each descriptor, respectively, increases the accuracy of surrogate models for melting point prediction compared to using the structural descriptors alone. The best model, based on ECFP4 and molecular orbital energies, predicts ionic liquid melting points with an average mean absolute error of 29 K and, unlike group contribution methods, which have achieved similar results, is applicable to any type of ionic liquid. [ABSTRACT FROM AUTHOR]

Photoelectron–photofragment coincidence (PPC) spectroscopy is used to study the photodetachment, photodissociation, and dissociative photodetachment (DPD) of I2Br−, IBr2−, I2Cl−, and ICl2− at 266 nm. The mixed trihalides are asymmetric analogs of the well-studied I3− anion, with distinguishable dissociation asymptotes and the potential for selective bond breaking. The high beam energy PPC spectrometer used in this study couples an electrospray ionization source, a hexapole accumulation ion trap, and a linear accelerator to produce a 21 keV beam of a particular trihalide. Total, stable, and dissociative photoelectron spectra have been recorded for all the anions, except ICl2− that does not photodetach at 266 nm. A bound ground state (X) is observed for all the anions, and a dissociative first excited (A) state is also seen for I2Br− and I2Cl− at low electron kinetic energies (eKE). A 258 nm photoelectron spectrum recorded for I2Br− and I2Cl− rules out autodetachment of a dipole-bound state as the origin of the low eKE feature. The threshold detachment energy (TDE) of I2X− to the X state of the radical is similar to I3−, whereas the TDE to the radical A state increases with substitution of iodine for a lighter halogen. Two-body DPD is observed for I2Br− and I2Cl−, resulting in IBr/ICl + I + e−. For IBr2− and ICl2−, the charge symmetric three-body photodissociation of [Br–I–Br]− and [Cl–I–Cl]− is seen yielding Br + Br and Br + Br*, and Cl + Cl and Cl + Cl* neutral fragments. Evidence for the minimum energy anion structure is observed in all cases, where the iodine atom is located at the center of the trihalide. [ABSTRACT FROM AUTHOR]

The low melting point of room temperature ionic liquids is usually explained in terms of the presence of bulky, low-symmetry, and flexible ions, with the first two factors related to the lattice energy while an entropic effect is attributed to the latter. By means of molecular dynamics simulations, the melting points of 1-ethyl-3-methyl-imidazolium hexafluorophosphate and 1-decyl-3-methyl-imidazolium hexafluorophosphate were determined, and the effect of the molecular flexibility over the melting point was explicitly computed by restraining the rotation of dihedral angles in both the solid and the liquid phases. The rotational flexibility over the bond between the ring and the alkyl chain affects the relative ordering of the anions around the cations and results in substantial effects over both the enthalpy and the entropy of melting. For the other dihedral angles of the alkyl group, the contributions are predominantly entropic and an alternating behavior was found. The flexibility of some dihedral angles has negligible effects on the melting point, while others can lead to differences in the melting point as large as 20 K. This alternating behavior is rationalized by the different probabilities of conformation defects in the crystal. [ABSTRACT FROM AUTHOR]

Rotationally resolved electronic spectra of two conformational isomers of jet-cooled indole-4-carboxylic acid (I4CA) and the deuterated forms of the acid (—COOD) and amide (—ND) groups have been obtained using a UV laser/molecular beam spectrometer. The in-plane orientation of the acid group defines the two lowest energy rotamers of I4CA. The S1 ← S0 origin bands of the two rotamers and four isotopologues have been fit to asymmetric rotor Hamiltonians in both electronic states. From the best-fit parameters, the positions of the H-atoms in the principal axis frames of each conformer have been determined and serve to unambiguously identify the syn forms (i.e., COH⋯O) of the cis and trans rotamers. The experimental S0 and S1 inertial parameters, hydrogen atom positions, and transition dipole moment (TDM) orientations are compared with the results of theoretical calculations. The TDM orientation indicates that the S1 state is the 1La state in contrast to most substituted indoles. The molecular orbital properties and natural charges are investigated to better understand the 1La/1Lb state reversal and the extent of photoinduced intramolecular charge transfer that impacts the rotamer-dependent fluorescence lifetimes. [ABSTRACT FROM AUTHOR]

Recent experiments have shown how nematically ordered tactoid shaped actin droplets can be reorganized and divided by the action of myosin molecular motors. In this paper, we consider how similar morphological changes can potentially be achieved under equilibrium conditions. Using simulations, both atomistic and continuum, and a simple macroscopic model, we explore how the nucleation dynamics, shape changes, and the final steady state of a nematic tactoid droplet can be modified by interactions with model adhesive colloids that mimic a myosin motor cluster. We show how tactoid reorganization may occur in an equilibrium colloidal-nematic setting. We then suggest based on the simple macroscopic model how the simulation models may be extended to potentially stabilize divided tactoids. [ABSTRACT FROM AUTHOR]

The influence of ring-puckering on the light-induced ring-opening dynamics of heterocyclic compounds was studied on the sample 5-membered ring molecules γ-valerolactone and 5H-furan-2-one using time-resolved photoelectron spectroscopy and ab initio molecular dynamics simulations. In γ-valerolactone, ring-puckering is not a viable relaxation channel and the only available reaction pathway is ring-opening, which occurs within one vibrational period along the C—O bond. In 5H-furan-2-one, the C=C double bond in the ring allows for ring-puckering which slows down the ring-opening process by about 150 fs while only marginally reducing its quantum yield. This demonstrates that ring-puckering is an ultrafast process, which is directly accessible upon excitation and which spreads the excited state wave packet quickly enough to influence even the outcome of an otherwise expectedly direct ring-opening reaction. [ABSTRACT FROM AUTHOR]

Molecular ions undergoing ultrafast conformational changes on the same time scale of water motions are of significant importance in condensed phase dynamics. However, the characterization of systems with fast molecular motions has proven to be both experimentally and theoretically challenging. Here, we report the vibrational dynamics of the non-degenerate (C12,C13)-oxalate anion, an ultrafast rotor, in aqueous solution. The infrared absorption spectrum of the (C12,C13)-oxalate ion in solution reveals two vibrational transitions separated by approximately 40 cm-1 in the 1500-1600 cm-1 region. These two transitions are assigned to vibrational modes mainly localized in each of the carboxylate asymmetric stretch of the ion. Two-dimensional infrared spectra reveal the presence and growth of cross-peaks between these two transitions which are indicative of coupling and population transfer, respectively. A characteristic time of sub-picosecond cross-peaks growth is observed. Ultrafast pump-probe anisotropy studies reveal essentially the same characteristic time for the dipole reorientation. All the experimental data are well modeled in terms of a system undergoing ultrafast population transfer between localized states. Comparison of the experimental observations with simulations reveal a reasonable agreement, although a mechanism including only the fluctuations of the coupling caused by the changes in the dihedral angle of the rotor, is not sufficient to explain the observed ultrafast population transfer. [ABSTRACT FROM AUTHOR]