The delocalized, anticorrelated component of pigment vibrations can drive nonadiabatic electronic energy transfer in photosynthetic light-harvesting antennas. In femtosecond experiments, this energy transfer mechanism leads to excitation of delocalized, anticorrelated vibrational wavepackets on the ground electronic state that exhibit not only 2D spectroscopic signatures attributed to electroni...

Closed expressions for nonadiabatic couplings are derived using the collective electronic oscillators (CEO) algorithm based on the time-dependent Hartree–Fock equations. Analytic derivatives allow the calculation of transition density matrices and potential surfaces at arbitrary nuclear geometries using a molecular dynamics trajectory that only requires a CEO calculation at a single configurati...

Light-driven molecular motors derived from chiral overcrowded alkenes are an important class of compounds in which sequential photochemical and thermal rearrangements result in unidirectional rotation of one part of the molecule with respect to another. Here, we employ anion photoelectron spectroscopy to probe the electronic structure and dynamics of a unidirectional molecular rotary motor anio...

The methods producing cold molecules from cold atoms tend to leave molecular ensembles with substantial residual internal energy. For instance, cesium molecules initially formed via photoassociation of cold cesium atoms are in several vibrational levels nu of the electronic ground state. We applied a broadband femtosecond laser that redistributes the vibrational population in the ground state v...

the high pressure behavior of the structural and electronic properties of kc1 is studied with use of the density functional pseudopotential method within local-density approximation. atzero pressure, the rocksalt phase is found to be lower in energy than cscl structure. however, we predict a phase transition into csci structure at a pressure of about 1.5 gpa. the calculated ground state propert...

Light-driven molecular motors derived from chiral overcrowded alkenes are an important class of compounds in which sequential photochemical and thermal rearrangements result in unidirectional rotation of one part of the molecule with respect to another. Here, we employ anion photoelectron spectroscopy to probe the electronic structure and dynamics of a unidirectional molecular rotary motor anio...

A global, analytical potential energy surface for the ground electronic state of HOBr has been determined using highly correlated multireference configuration interaction wave functions and explicit basis set extrapolations of large correlation consistent basis sets. The ab initio data have been fit to an analytical functional form that accurately includes both the HOBr and HBrO minima, as well...

Electronic charge rearrangement between components of a heterostructure is the fundamental principle to reach electronic ground state. It acknowledged that density state distribution governs amount transfer, but notable dependence on temperature not yet considered, particularly for weakly interacting systems. Here, it experimentally observed ground-state transfer in van der Waals formed by mono...

Controlling the excited-state properties of light driven molecular machines is crucial to achieving high efficiency and directed functionality. A key challenge in achieving control lies in unravelling the complex photodynamics and especially in identifying the role played by dark states. Here we use the structure sensitivity and high time resolution of UV-pump/IR-probe spectroscopy to build a d...