Nonadiabatic molecular dynamics simulation: An approach based on quantum measurement picture

Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for nonadiabatic molecular dynamics simulations. The new protocol provides a natural interface between the separate quantum and classical treatments, without invoking artificial surface hopping algorithm. Moreover, it also bridges two widely adopted nonadiabatic dynamics methods, the Ehrenfest mean-field theory and the trajectory surface-hopping method. Excellent agreement with the exact results is illustrated with representative model systems, including the challenging ones for traditional methods

Improved Memory Truncation Scheme for Quasi-Adiabatic Propagator Path Integral via Influence Functional Renormalization

Accurately simulating non-Markovian quantum dynamics in system-bath coupled problems remains challenging. In this work, we present a novel memory truncation scheme for the iterative Quasi-Adiabatic Propagator Path Integral (iQuAPI) method to improve accuracy. Conventional memory truncation in iQuAPI discards all influence functional beyond a certain time interval, which is not effective for problems with a long memory time. Our proposed scheme selectively retains the most significant parts of the influence functional using the density matrix renormalization group algorithm. We validate the effectiveness of our scheme through simulations of the spin-boson model across various parameter sets, demonstrating faster convergence and improved accuracy compared to the conventional scheme. Our findings suggest that the new memory truncation scheme significantly advances the capabilities of iQuAPI for problems with a long memory time.Comment: 10 pages, 4 figure

Effects of Antimicrobial Peptide Revealed by Simulations: Translocation, Pore Formation, Membrane Corrugation and Euler Buckling

We explore the effects of the peripheral and transmembrane antimicrobial peptides on the lipid bilayer membrane by using the coarse grained Dissipative Particle Dynamics simulations. We study peptide/lipid membrane complexes by considering peptides with various structure, hydrophobicity and peptide/lipid interaction strength. The role of lipid/water interaction is also discussed. We discuss a rich variety of membrane morphological changes induced by peptides, such as pore formation, membrane corrugation and Euler buckling

Exciton-Phonon Interaction Model for Singlet Fission in Prototypical Molecular Crystals

In singlet fission (SF), a spin-conserving splitting of one singlet exciton into two triplet excitation states, the transition between localized electronic states can be controlled and modulated by delocalized lattice phonons. In this work, we built an exciton–phonon (ex–ph) interaction model accounting local electronic states coupled with both local molecular vibrations and low frequency intermolecular phonon modes for SF in crystalline tetracene and rubrene. On the basis of the calculated electronic couplings at the equilibrium structure of the molecular dimer, a superexchange path for SF was found for tetracene while couplings between the triplet pair (TT) state and other diabatic states are zero for rubrene due to the high symmetry. Our further ex–ph spectral density analysis and quantum dynamics simulation based on our ex–ph interaction model suggested a thermal-activated mechanism for SF in rubrene crystal via symmetry breaking by nuclear vibration, which is in agreement with recent experiments. It is also shown that thermal fluctuations of electronic couplings in both tetracene and rubrene are mostly in the same order of magnitude at room temperature, and this could be one of the reasons for both tetracene and rubrene to exhibit SF time scales within a close range (hundreds to thousands of femtoseconds) in experiments

Dynamics of Oxygen-Independent Photocleavage of Blebbistatin as a One-Photon Blue or Two-Photon Near-Infrared Light-Gated Hydroxyl Radical Photocage

Development of versatile, chemically tunable photocages for photoactivated chemotherapy (PACT) represents an excellent opportunity to address the technical drawbacks of conventional photodynamic therapy (PDT) whose oxygen-dependent nature renders it inadequate in certain therapy contexts such as hypoxic tumors. As an alternative to PDT, oxygen free mechanisms to generate cytotoxic reactive oxygen species (ROS) by visible light cleavable photocages are in demand. Here, we report the detailed mechanisms by which the small molecule blebbistatin acts as a one-photon blue light-gated or two-photon near-infrared light-gated photocage to directly release a hydroxyl radical (•OH) in the absence of oxygen. By using femtosecond transient absorption spectroscopy and chemoselective ROS fluorescent probes, we analyze the dynamics and fate of blebbistatin during photolysis under blue light. Water-dependent photochemistry reveals a critical process of water-assisted protonation and excited state intramolecular proton transfer (ESIPT) that drives the formation of short-lived intermediates, which surprisingly culminates in the release of •OH but not superoxide or singlet oxygen from blebbistatin. CASPT2//CASSCF calculations confirm that hydrogen bonding between water and blebbistatin underpins this process. We further determine that blue light enables blebbistatin to induce mitochondria-dependent apoptosis, an attribute conducive to PACT development. Our work demonstrates blebbistatin as a controllable photocage for •OH generation and provides insight into the potential development of novel PACT agents