Display omitted
•The Singular Value Decomposition (SVD) and the Schmidt decomposition of an entangled electron-nuclear wave function.•The leading terms of the SVD provide a compact expression of the ...Born-Huang expansion of the entangled electron-nuclear wave function.•The time evolution of the entanglement of the wave function following upon an ultrafast excitation is determined.•The contribution of the pumping of excited states to entanglement is quantified.•The contributions of the non-adiabatic interactions to entanglement are evaluated.
Ultrafast pumping displaces both electrons and nuclei from equilibrium so that the wave function is a double sum of separable terms for the dynamics of the electrons and nuclei. We convert the double sum into a single one by a matricization of the wave function and then generate an exact separable expression for the entangled molecular wave function. A most compact approximation with a minimum number of terms is obtained via Singular Value Decomposition. LiH and N2 are used as an illustration: the two differ in their adiabatic electronic dynamics in the energy range accessible by a UV pulse.
We report on fully quantum electronic-nuclear dynamics following sudden ionization from the neutral in the three lowest electronic states of the CH4 + and CD4 + cations. There is a strong Jahn–Teller ...effect in the Franck–Condon region, and we employ two nuclear degrees of freedom that span the internal coordinates involved in the Jahn–Teller coupling. The initial state results from tunneling ionization by a strong IR field which coherently pumps the three lowest states of the cation, D0, D1, and D2. The quantum dynamical simulations show that a strong isotope effect occurs when the ionization significantly accesses the D2 state of the cation in the Franck–Condon region. The computed isotope effect is larger than expected on the basis of the effective mass ratio. The strong effect is due to fast oscillations of the electronic coherences between the D2 and the D1 and D0 electronic states and their modulation by the nonadiabatic couplings before a significant onset of nuclear motion. The magnitude of the effect is similar to the one that we previously reported for a sudden photoionization process. A strong isotope effect has been observed in high harmonic spectroscopy studies of the very short time dynamics Jahn–Teller structural rearrangement of the methane cation upon sudden ionization.
Human T-cell leukemia virus type-1 (HTLV-1) is the first pathogenic retrovirus discovered in human. Although HTLV-1-induced diseases are well-characterized and linked to the encoded Tax-1 ...oncoprotein, there is currently no strategy to target Tax-1 functions with small molecules. Here, we analyzed the binding of Tax-1 to the human homolog of the drosophila discs large tumor suppressor (hDLG1/SAP97), a multi-domain scaffolding protein involved in Tax-1-transformation ability. We have solved the structures of the PDZ binding motif (PBM) of Tax-1 in complex with the PDZ1 and PDZ2 domains of hDLG1 and assessed the binding of 10 million molecules by virtual screening. Among the 19 experimentally confirmed compounds, one systematically inhibited the Tax-1-hDLG1 interaction in different biophysical and cellular assays, as well as HTLV-1 cell-to-cell transmission in a T-cell model. Thus, our work demonstrates that interactions involving Tax-1 PDZ-domains are amenable to small-molecule inhibition, which provides a framework for the design of targeted therapies for HTLV-1-induced diseases.
•HTLV Tax-1/hDLG1 interaction is an important therapeutic target.•Full characterization of Tax-1/hDLG1 PDZ1 and PDZ2 interactions are reported.•Crystallization of PDZ1 and PDZ2 complexed with Tax-1 PBM•Identification of small molecule inhibitors for Tax-1/PDZ interaction.•Small molecule 3 inhibits Tax-1-PDZ interaction thereby blocking HTLV-1 cell to cell transmission and viral replication.
A detailed analysis of available in situ and remotely sensed N2O and CH4 data measured in the 1999/2000 winter Arctic vortex has been performed in order to quantify the temporal evolution of vortex ...descent. Differences in potential temperature (theta) among balloon and aircraft vertical profiles (an average of 19-23 K on a given N2O or CH4 isopleth) indicated significant vortex inhomogeneity in late fall as compared with late winter profiles. A composite fall vortex profile was constructed for 26 November 1999, whose error bars encompassed the observed variability. High-latitude extravortex profiles measured in different years and seasons revealed substantial variability in N2O and CH4 on theta surfaces, but all were clearly distinguishable from the first vortex profiles measured in late fall 1999. From these extravortex-vortex differences we inferred descent prior to 26 November: as much as 397 plus or minus 15 K (lsigma) at 30 ppbv N2O and 640 ppbv CH4, and falling to 28 plus or minus 13 K above 200 ppbv N2O and 1280 ppbv CH4. Changes in theta were determined on five N2O and CH4 isopleths from 26 November through 12 March, and descent rates were calculated on each N2O isopleth for several time intervals. The maximum descent rates were seen between 26 November and 27 January: 0.82 plus or minus 0.20 K/day averaged over 50- 250 ppbv N2O. By late winter (26 February to 12 March), the average rate had decreased to 0.10 plus or minus 0.25 K/day. Descent rates also decreased with increasing N2O; the winter average (26 November to 5 March) descent rate varied from 0.75 plus or minus 0.10 K/day at 50 ppbv to 0.40 plus or minus 0.11 K/day at 250 ppbv. Comparison of these results with observations and models of descent in prior years showed very good overall agreement. Two models of the 1999/2000 vortex descent, SLIMCAT and REPROBUS, despite theta offsets with respect to observed profiles of up to 20 K on most tracer isopleths, produced descent rates that agreed very favorably with the inferred rates from observation.
PDF