摘要：In(relativistic)electronic structure methods,the quaternion matrix eigenvalue problem and the linear response(Bethe-Salpeter)eigenvalue problem for excitation energies are two frequently encoun-tered structured eigenvalue *** the former problem was thoroughly studied,the later problem in its most general form,namely,the complex case without assuming the positive definiteness of the electronic Hessian,was not fully *** view of their very similar mathematical structures,we examined these two problems from a unified point of *** showed that the identification of Lie group structures for their eigenvectors provides a framework to design diagonalization algorithms as well as numerical optimizations techniques on the corresponding *** using the same reduction algorithm for the quaternion matrix eigenvalue problem,we provided a necessary and sufficient condition to characterize the different scenarios,where the eigenvalues of the original linear response eigenvalue problem are real,purely imaginary,or *** result can be viewed as a natural generalization of the well-known condition for the real matrix case.

摘要：Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of ***,the underlying mechanism remains *** ab initio nonadiabatic(NA)molecular dynamics combined with time-domain density functional simulations,we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic *** nuclear motions simultaneously increase the decoherence time,which is overcome by the reduced NA coupling,extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3,which occurs within sub-nanosecond and agrees with *** study established the mechanism for the experimentally reported prolonged excited-state lifetime,providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.

摘要：Understanding the excited state dynamics of donor-acceptor(D-A)complexes is of fundamental importance both experimentally and ***,we have first explored the photoinduced dynamics of a recently synthesized paddle-wheel BODIPY-hexaoxatriphenylene(BODIPY is the abbreviation for BF_(2)-chelated dipyrromethenes)conjugates D-A complexes with the combination of both electronic structure calculations and nonadiabatic dynamics *** the basis of computational results,we concluded that the BODIPY-hexaoxatriphenylene(BH)conjugates will be promoted to the local excited(LE)states of the BODIPY fragments upon excitation,which is followed by the ultrafast exciton transfer from LE state to charge transfer(CT).Instead of the photoinduced electron transfer process proposed in previous experimental work,such a exciton transfer process is accompanied with the photoinduced hole transfer from BODIPY to ***,solvent effects are found to play an important role in the photoinduced ***,the hole transfer dynamics is accelerated by the acetonitrile solvent,which can be ascribed to significant influences of the solvents on the charge transfer states,*** energy gaps between LE and CT excitons are reduced greatly and the non-adiabatic couplings are increased in the *** present work not only provides valuable insights into the underlying photoinduced mechanism of BH,but also can be helpful for the future design of novel donor-acceptor conjugates with better optoelectronic performance.

摘要：The severe bulk recombination and sluggish oxygen evolution reaction(OER)dynamics of photoanodes severely restrict the application of photoelectrochemical(PEC)*** solve these two problems,crystallographic facet orientation and cocatalyst emergence with a high-quality photoanode/cocatalyst interface were realized through an air annealing-assisted strategy to treat atomic layer deposition(ALD)-modified SnSnanosheet *** on experimental observations and theoretical calculations,the reduced(001)crystal facet of SnSdecreases the recombination of photogenerated carriers in the bulk and improves the carrier separation of the ***,the unexpectedly formed ZnTiOSfilm decreases the overpotential of the surface OER,reduces interface recombination,and extends the carrier *** synergistic effects lead to significantly enhanced PEC performance,with a high photocurrent density of 1.97 mA cm^(-2)at 1.23 V *** hydrogen electrode(RHE)and a low onset potential of 0.21 V ***,which are superior to reported mostly SnS-based photoanodes.

摘要：Excited-state double proton transfer(ESDPT)is a controversial issue which has long been plagued with theoretical and experimental ***,we took 1,8-dihydroxy-2-naphthaldehyde(DHNA)as a prototype and used combined complete active space selfconsistent field(CASSCF)and multi-state complete active-space second-order perturbation(MS-CASPT2)methods to investigate ESDPT and excited-state deactivation pathways of *** different tautomer minima of S1-ENOL,S1-KETO-1,and S1-KETO-2 and two crucial conical intersections of S1 S0-KETO-1 and S1 S0-KETO-2 in and between the S0 and S1 states were obtained.S1-KETO-1 and S1-KETO-2 should take responsibility for experimentally observing dual-emission *** addition,two-dimensional potential energy surfaces(2 D-PESs)and linear interpolated internal coordinate paths connecting relevant structures were calculated at the MS-CASPT2//CASSCF level and confirmed a stepwise ESDPT ***,the first proton transfer from S1-ENOL to S1-KETO-1 is barrierless,whereas the second one from S1-KETO-1 to S1-KETO-2 demands a barrier of ca.6.0 kcal/*** linear interpolated internal coordinate path connecting S1-KETO-1(S1-KETO-2)and S_(1) S0-KETO-1(S1 S0-KETO-2)is uphill with a barrier of ca.12.0 kcal/mol,which will trap DHNA in the S_(1) state while therefore enabling dual-emission *** the other hand,the S1/S0 conical intersections would also prompt the S_(1) system to decay to the S_(0) state,which could be to certain extent suppressed by locking the rotation of the C5-C8-C9-O10 dihedral *** mechanistic insights are not only helpful for understanding ESDPT but also useful for designing novel molecular materials with excellent photoluminescent performances.