Spin-orbit coupling and vibronic coupling are both closely related to orbital degeneracy of electronic states. Both types of coupling play significant roles in determining properties of heavy element compounds and shall be treated on the same footing. In this work, we derive a unified one-electron Hamiltonian formalism for spin-orbit and vibronic interactions for systems in all axial symmetries. The one-electron formalism is usually adequate as spin-orbit interaction can often be approximated as...
A detailed experimental study on reversible photo-induced intramolecular charge separation is presented based on NMR detection of Chemically Induced Dynamic Nuclear Polarization (CIDNP). From variation of such polarization with the external magnetic field the coupling constants of isotropic and anisotropic hyperfine interaction at individual 13C sites are measured in the short-lived charge separated state of dyad molecules composed of donor-bridge-acceptor parts. The objects of study were rigid ...
We present a comparison of the photoionization dynamics of the 4d shell of XeF2 from threshold to 250 eV to those of the prototypical 4d shell of atomic Xe. The new experimental data include spin–orbit and ligand-field-resolved partial cross sections, photoelectron angular distributions, branching fractions, and lifetime widths for the 4d-hole states. The spin–orbit branching fractions and angular distributions are remarkably similar to the corresponding distributions from atomic Xe across a bro...
An accurate atomistic treatment of aqueous solid–liquid interfaces necessitates the explicit description of interfacial water ideally via ab initio molecular dynamics simulations. Many applications, however, still rely on static interfacial water models, e.g., for the computation of (electro)chemical reaction barriers and focus on a single, prototypical structure. In this work, we systematically study the relation between density functional theory-derived static and dynamic interfacial water mod...
A new time-domain simulation protocol of two-dimensional electronic spectra with photocurrent detection is presented. Time-dependent density functional theory for open systems at finite temperature is applied to evaluate the photocurrent response to four laser pulses, and a non-perturbative phase-matching approach is implemented to extract the fourth-order photocurrent signal with a desired phase-matching condition. Simulations for an open three-level model indicates that transition dipoles inte...
#1Sina Lewis(CU: University of Colorado Boulder)H-Index: 1
#2Kori Smyser(CU: University of Colorado Boulder)H-Index: 1
Last. Joel D. Eaves(CU: University of Colorado Boulder)H-Index: 16
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Short coherence times present a primary obstacle in quantum computing and sensing applications. In atomic systems, clock transitions (CTs), formed from avoided crossings in an applied Zeeman field, can substantially increase coherence times. We show how CTs can dampen intrinsic and extrinsic sources of quantum noise in molecules. Conical intersections between two periodic potentials form CTs in electron paramagnetic resonance experiments of the spin-polarized singlet fission photoproduct. We rep...
Last. Frank Neese(MPG: Max Planck Society)H-Index: 123
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A factorization of the matrix elements of the Dyall Hamiltonianin N-electron valence state perturbation theory (NEVPT2) allowing their evaluation with a computational effort comparableto the one needed for the construction of the third-order reduced density matrix at the most is presented.Thus, the computational bottleneck arising from explicit evaluation of the fourth-order densitymatrix is avoided. It is also shown that the residual terms arising in case of an approximate CASCI solutionand con...
In the rotational spectroscopy community, several popular codes are available to treat multiple internal rotors in a molecule. In terms of the pros and the cons of each code, it often is a difficult task to decide which program to apply to a specific internal rotation problem. We faced this issue when dealing with the spectroscopic fingerprint of 4-methylacetophenone (4MAP), recently investigated in the microwave region, which we here extend into the millimeterwave region. The methyl group attac...
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