Molecular Photochemistry: Recent Developments in Theory

Mai, Sebastian; González, Leticia

doi:10.1002/anie.201916381

Cited by 123 publications

(149 citation statements)

References 226 publications

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“… 33 An alternative to low-dimensional quantum dynamics is the use of trajectory SH methods. 34 In SH, the PESs are computed on-the-fly, i.e., requiring only electronic structure calculations at the present geometry of the molecule. Although such a procedure renders possible the simulation of the early femtosecond (fs) dynamics of transition-metal complexes, 35 , 36 it is computationally very demanding.…”

Section: Methodsmentioning

confidence: 99%

Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer

et al. 2020

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The electronic excited states of the iron(II) complex [Fe II (tpy)(pyz-NHC)] 2+ [tpy = 2,2′:6′,2″-terpyridine; pyz-NHC = 1,1′-bis(2,6-diisopropylphenyl)pyrazinyldiimidazolium-2,2′-diylidene] and their relaxation pathways have been theoretically investigated. To this purpose, trajectory surface-hopping simulations within a linear vibronic coupling model including a 244-dimensional potential energy surface (PES) with 20 singlet and 20 triplet coupled states have been used. The simulations show that, after excitation to the lowest-energy absorption band of predominant metal-to-ligand charge-transfer character involving the tpy ligand, almost 80% of the population undergoes intersystem crossing to the triplet manifold in about 50 fs, while the remaining 20% decays through internal conversion to the electronic ground state in about 300 fs. The population transferred to the triplet states is found to deactivate into two different regions of the PESs, one where the static dipole moment is small and shows increased metal-centered character and another with a large static dipole moment, where the electron density is transferred from the tpy to pyz-NHC ligand. Coherent oscillations of 400 fs are observed between these two sets of triplet populations, until the mixture equilibrates to a ratio of 60:40. Finally, the importance of selecting suitable normal modes is highlighted—a choice that can be far from straightforward in transition-metal complexes with hundreds of degrees of freedom.

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Section: Methodsmentioning

confidence: 99%

Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer

et al. 2020

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“…44 Very large discrepancies with the experiments were encountered when computing the emission transitions for the neutral forms of HINA and its analogues. Indeed, an excited-state intramolecular proton-transfer process (ESIPT) 23,[45][46][47] likely occurs for these substances ( Figure S73 †). An intramolecular ESIPT may also explain the large discrepancies seen between the expected pH-dependent deprotonation of the excited state based on calculated pKa2* values, and the "ground-state like" protonation status observed in fluorescence experiments.…”

Section: Resultsmentioning

confidence: 99%

Discovery of a size-record breaking green-emissive fluorophore: small, smaller, HINA

et al. 2021

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“…30 We refer interested readers to several recent reviews on the state-of-the-art of WF-based and DFT-based QC methods. 28,[31][32][33][34] A brief summary of the two techniques can be also found in Data S1.…”

Section: Electronic Structure Methodsmentioning

confidence: 99%

iSPECTRON: A simulation interface for linear and nonlinear spectra with ab‐initio quantum chemistry software

et al. 2021

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We introduce iSPECTRON, a program that parses data from common quantum chemistry software (NWChem, OpenMolcas, Gaussian, Cobramm, etc.), produces the input files for the simulation of linear and nonlinear spectroscopy of molecules with the Spectron code, and analyzes the spectra with a broad range of tools. Vibronic spectra are expressed in term of the electronic eigenstates, obtained from quantum chemistry computations, and vibrational/bath effects are incorporated in the framework of the displaced harmonic oscillator model, where all required quantities are computed at the Franck-Condon point. The program capabilities are illustrated by simulating linear absorption, transient absorption and two dimensional electronic spectra of the pyrene molecule. Calculations at two levels of electronic structure theory, time-dependent density functional theory (with NWChem) and RASSCF/ RASPT2 (with OpenMolcas) are presented and compared where possible. The iSPECTRON program is available online at https://github.com/ispectrongit/ iSPECTRON/ and distributed open source under the terms of the Educational Community License version 2.0 (ECL 2.0).

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Molecular Photochemistry: Recent Developments in Theory

Cited by 123 publications

References 226 publications

Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer

Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer

Discovery of a size-record breaking green-emissive fluorophore: small, smaller, HINA

iSPECTRON: A simulation interface for linear and nonlinear spectra with ab‐initio quantum chemistry software

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