Trevinoniebuhr2547

The C2Bg band is also affected, but to a lesser extent. this website The adiabatic minima of the D2Au and E2Ag states are almost degenerate, and the vibronic interaction between these states is considerable. The potential energy surface of the D2Au state is predicted to have a double-minimum shape with respect to the au deformations of the molecular structure. The irregular vibrational structure of the resulting single photoelectron band reflects the non-adiabatic nuclear dynamics occurring on the two coupled potential energy surfaces above the energy of their conical intersection.Path reweighting is a principally exact method to estimate dynamic properties from biased simulations-provided that the path probability ratio matches the stochastic integrator used in the simulation. Previously reported path probability ratios match the Euler-Maruyama scheme for overdamped Langevin dynamics. Since molecular dynamics simulations use Langevin dynamics rather than overdamped Langevin dynamics, this severely impedes the application of path reweighting methods. Here, we derive the path probability ratio ML for Langevin dynamics propagated by a variant of the Langevin Leapfrog integrator. This new path probability ratio allows for exact reweighting of Langevin dynamics propagated by this integrator. We also show that a previously derived approximate path probability ratio Mapprox differs from the exact ML only by O(ξ4Δt4) and thus yields highly accurate dynamic reweighting results. (Δt is the integration time step, and ξ is the collision rate.) The results are tested, and the efficiency of path reweighting is explored using butane as an example.Recently, applications of swept-frequency pulses proved to be a useful approach to circumvent the problem of limited excitation bandwidth in pulsed ESR posed by conventional pulses. Here, we present a chirped excitation sequence, CHirped ORdered pulses for Ultra-broadband Spectroscopy (CHORUS), for ultra-broadband ESR spectroscopy. It will be demonstrated that the application of this sequence can address the problems of excitation non-uniformity and sensitivity to instrumental instabilities to a greater extent compared to the current state of the art. This sequence is highly promising for finding applications beyond single excitation in many ESR experiments. Theoretical and experimental results for the proposed method are presented along with calibration strategies for experimental implementation.The first electronic hyperpolarizability (β) of phenol blue (PB) in several solvents in a wide range of dielectric constants is investigated using the density functional theory (DFT). The reliability of various exchange-correlation functionals is assessed by a comparison to reference Møller-Plesset second-order perturbation theory (MP2) calculations. The equilibrium geometry of PB in each solvent is obtained by using the average solvent electrostatic configuration/free energy gradient method, which performs optimizations on the free energy hyper-surface by employing iteratively the sequential quantum mechanics/molecular mechanics methodology. The dependence of β on the bond length alternation (BLA) coordinate is rationalized by means of the two-level model. Within the employed exchange-correlation functionals, the LC-BLYP functional shows the best performance for describing the static and dynamic MP2 results of β, which increases as the BLA diminishes, reaching a maximum in an intermediate value of BLA. The results also illustrate the role played by the difference between the ground- and excited-state dipole moments (Δμ) in determining the hyperpolarizability behavior in solution. Particularly, in the aqueous solution case, Δμ goes to around zero when BLA is near zero, leading to an abrupt decline in the β value. The DFT results of this study, therefore, indicate a clear relationship between the first hyperpolarizability and the BLA coordinate for the PB in solution, in agreement with experiment.We employ theoretically "exact" and numerically "accurate" Beyond Born-Oppenheimer (BBO) treatment to construct diabatic potential energy surfaces (PESs) of the benzene radical cation (C6H6+) for the first time and explore the workability of the time-dependent discrete variable representation (TDDVR) method for carrying out dynamical calculations to evaluate the photoelectron (PE) spectra of its neutral analog. Ab initio adiabatic PESs and nonadiabatic coupling terms are computed over a series of pairwise normal modes, which exhibit rich nonadiabatic interactions starting from Jahn-Teller interactions and accidental conical intersections/seams to pseudo Jahn-Teller couplings. Once the electronic structure calculation is completed on the low-lying five doublet electronic states (X̃2E1g, B̃2E2g, and C̃2A2u) of the cationic species, diabatization is carried out employing the adiabatic-to-diabatic transformation (ADT) equations for the five-state sub-Hilbert space to compute highly accurate ADT angles, and thereby, single-valued, smooth, symmetric, and continuous diabatic PESs and couplings are constructed. Subsequently, such surface matrices are used to perform multi-state multi-mode nuclear dynamics for simulating PE spectra of benzene. Our theoretical findings clearly depict that the spectra for X̃2E1g and B̃2E2g-C̃2A2u states obtained from BBO treatment and TDDVR dynamics exhibit reasonably good agreement with the experimental results as well as with the findings of other theoretical approaches.Solid-state electrolyte materials with superior lithium ionic conductivities are vital to the next-generation Li-ion batteries. Molecular dynamics could provide atomic scale information to understand the diffusion process of Li-ion in these superionic conductor materials. Here, we implement the deep potential generator to set up an efficient protocol to automatically generate interatomic potentials for Li10GeP2S12-type solid-state electrolyte materials (Li10GeP2S12, Li10SiP2S12, and Li10SnP2S12). The reliability and accuracy of the fast interatomic potentials are validated. With the potentials, we extend the simulation of the diffusion process to a wide temperature range (300 K-1000 K) and systems with large size (∼1000 atoms). Important technical aspects such as the statistical error and size effect are carefully investigated, and benchmark tests including the effect of density functional, thermal expansion, and configurational disorder are performed. The computed data that consider these factors agree well with the experimental results, and we find that the three structures show different behaviors with respect to configurational disorder.