Steady and Time-Resolved Photoelectron Spectra Based on Nuclear Ensembles

Arbelo-González, Wilmer; Crespo‐Otero, Rachel; Barbatti, Mario

doi:10.1021/acs.jctc.6b00704

Cited by 44 publications

(63 citation statements)

References 85 publications

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“…The distribution of kinetic energies (or electron binding energies) then reflects the probability of a given geometry

σ true(E_{k} true) \sim \sum_{i} \int ϱ (|, \vec{R}) f_{i} true(E true) δ (|, E - E_{B . i} - E_{k}) d \vec{R},

where

σ true(E_{k} true)

is the cross section for emitting the electron with a kinetic energy E k . Equation (the so called reflection principle (RP)) provides a pictorial classical view on electronic spectroscopy, representing at the same time a well‐defined approximation of the quantum‐mechanical cross section . The spectrum in principle depends on the photon energy via the oscillator strength; this dependence is ignored here, assuming that all the electronic factors are equal for all transitions and that they are geometry independent.…”

Section: Methodsmentioning

confidence: 99%

“…[55,56] Equation (3) (the so called reflection principle (RP)) provides a pictorial classical view on electronic spectroscopy, representing at the same time a well-defined approximation of the quantum-mechanical cross section. [46,57,58] The spectrum in principle depends on the photon energy via the oscillator strength; this dependence is ignored here, assuming that all the electronic factors are equal for all transitions and that they are geometry independent. Such an approximation is reasonable for high-energy X-ray photons.…”

Section: Methodsmentioning

confidence: 99%

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Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

2017

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An efficient approach for quantitative modeling of liquid phase photoelectron spectra, reorganization energies, and redox potentials with DFT-based molecular dynamics simulations is presented. The method is based on a large scale cluster-continuum approach combined with the so-called reflection principle (RP). Finite size clusters of solute molecules with solvating water molecules are at first generated using either classical molecular dynamics or molecular dynamics with a quantum thermostat which accounts for nuclear quantum effects. In the next step, the electron binding energies are calculated. Finite-size corrections for (i) positions of electron binding energies and (ii) width of the spectrum are evaluated via a dielectric continuum approach. The performance of such a reflection principle with additional broadening approach (RP-AB) for oxidation of multiply charged iron anions, [Fe(CN) ] and [Fe(CN) ] is demonstrated. The role of nuclear quantum effects is discussed as well as the relation between spectroscopic data and electrochemical quantities. Results are compared with recent liquid photoemission experiments, explaining the obstacles for applying liquid phase photoemission spectroscopy as a direct method for obtaining absolute redox potentials and suggesting a way to overcome them. © 2017 Wiley Periodicals, Inc.

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“…The distribution of kinetic energies (or electron binding energies) then reflects the probability of a given geometry

σ true(E_{k} true) \sim \sum_{i} \int ϱ (|, \vec{R}) f_{i} true(E true) δ (|, E - E_{B . i} - E_{k}) d \vec{R},

where

σ true(E_{k} true)

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

2017

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“…These auxiliary functions have been used for the calculation of various other properties including spinorbit couplings, 170,373,386 transition dipole moments, 362,387 nonadiabatic coupling vectors, 362,388 and Dyson orbitals. [389][390] 5…”

Section: Calculation Of Couplingsmentioning

confidence: 99%

“…The nuclear ensemble approach (NEA) can be explored to simulate different steady and time-resolved spectroscopic techniques, including inhomogeneous broadening. [391][392] Usually, working as a post-processing of the dynamics results, the nuclear ensembles have been applied for simulations of a large variety of time-resolved spectra, including twodimensional, differential transmission, 393 photoelectron, 24,217,325,[389][390][394][395][396][397] ultrafast Auger, 24,398 and X-ray photo-scattering 24 spectroscopies. These developments and applications have been based on a broad range of approximations and electronic structure methods, from simple estimates of transition probabilities 24,325,387,395,[399][400][401] to involved modeling of transition moments.…”

Section: Spectroscopic Simulations Based On Na-mqc Dynamicsmentioning

confidence: 99%

“…Moreover, NEWTON-X counts on modules for spectrum simulations based on the nuclear ensemble approach (Section 5), enabling simulations of steady and time-resolved absorption, emission, and photoionization spectra. 390,406 A recently developed external code, PYSOC, enables calculations of spin-orbit couplings with LR-TDDFT. 373 COBRAMM from Garavelli and coworkers is tailored to perform MCSCF/MM simulations of organic and biomolecular systems within the FSSH approximation.…”

Section: Software Resources For Na-mqc Dynamicsmentioning

confidence: 99%

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Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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