Non-adiabatic dynamics of the entanglement entropy in a symmetry-breaking Haldane insulator

We study the non-adiabatic dynamics of a typical symmetry-protected topological phase-the Haldane insulator phase with broken bond-centered inversion. By continuously breaking the middle chain, we find the gap closes at a critical point in the deep Haldane insulator regime with a change of particle number partition of the left or right system. The adiabatic evolution fails at this critical point and we show how to predict the dynamics of the entanglement entropy near this point using a two-level model. These results show that one can find a critical regime where the entanglement measurement is relatively robust against perturbation that breaks the protecting symmetries in the Haldane insulator. This is in contrast to the common belief that the symmetry-protected topological phases are fragile without the protecting symmetries.

Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2

The Born–Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X2Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment–theory disagreement concerning the branching ratio of the two electronic quenching channels.

Internal Conversion of the Anionic GFP Chromophore: In and Out of the I-twisted S1/S0 Conical Intersection Seam

<p>The functional diversity of the green fluorescent protein (GFP) family is intimately connected to the interplay between competing photo-induced transformations of the chromophore motif, anionic <i>p</i>-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI^–). Its propensity to undergo <i>Z/E</i> photoisomerization following excitation to the S₁(pp^*) state is of particular importance for super-resolution microscopy and emerging opportunities in optogenetics. However, key dynamical aspects of this process and its range of tunability still remain elusive. Here, we investigate the internal conversion behavior intrinsic to HBDI^– with focus on competing deactivation pathways, rate and yield of photoisomerization. Based on non-adiabatic dynamics simulations, we confirm that non-selective progress along the two bridge-torsional (i.e., phenolate, P, or imidazolinone, I) pathways can account for the three decay constants reported experimentally, leading to competing ultrafast relaxation along the I-twisted pathway and S₁trapping along the P-torsion. The majority of the population (~70%) is transferred to S₀ in the vicinity of two near-symmetry-related minima on the I-twisted intersection seam (MECI-Is). Despite their reactant-biased topographies, our account of inertial effects suggests that isomerization not only occurs as a thermal process on the vibrationally hot ground state but also as a direct photoreaction with a total quantum yield of ~40%.</p><p>By comparing the non-adiabatic dynamics to a photoisomerization committor analysis, we provide a detailed mapping of the intrinsic photoreactivity and dynamical behavior of the two MECI-Is. Our work offers new insight into the internal conversion process of HBDI^– that enlightens principles for the design of chromophore derivatives and protein variants with improved photoswitching properties.</p>