Some recent developments of high-order response theory

Luo, Yi; Jonsson, Dan; Norman, Patrick; Ruud, Kenneth; Vahtras, Olav; Минаев, Б. Ф.; Ågren, Hans; Rizzo, Antonio; Mikkelsen, Kurt V.

doi:10.1002/(sici)1097-461x(1998)70:1<219::aid-qua19>3.0.co;2-9

Cited by 34 publications

(20 citation statements)

References 86 publications

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“…, is in a good agreement with ab initio result of the quadratic response (QR) calculation with large active space at the multiconfiguration self‐consistent field (MC SCF) level (4.6 × 10 −4 μ B ). The semiempirical value is also in a reasonable accord with the vertical transition moment |μ a − X ,1 | = 0.0025 μ B , calculated by QR method . The |μ a − X ,1 l | term is larger than the |μ b − X ,1 l | magnetic orbital contribution by 6.3 times.…”

Section: Analysis Of Intensity Of the Dioxygen Weak Bands In Gas Phasesupporting

confidence: 85%

“…But still the a − X ,1 transition is very weak; the radiative rate constant for spontaneous emission (or Einstein A coefficient) calculated with the magnetic dipole transition moment, Eq. , provides k a → X = 8.3 × 10 −5 s −1 , being close to results of QR methods . The ab initio calculations of Klotz et al give |μ a − X ,1 | = 0.00376 μ B and k a − X = 1.897 × 10 −4 s −1 , which is in a reasonable agreement with the most recent experimental value of Newman et al (2.19 × 10 −4 s −1 ) …”

Section: Analysis Of Intensity Of the Dioxygen Weak Bands In Gas Phasesupporting

confidence: 85%

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Dioxygen spectra and bioactivation

Minaev

Murugan

Ågren

2013

Int J of Quantum Chemistry

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Intensities of spin-forbidden transitions in electronic absorption and emission spectra of molecular oxygen are analyzed in order to understand the key mechanisms of spinstates mixing induced by spin-orbit coupling (SOC) and the ways to overcome spin prohibition for various photophysical and biochemical processes. Multireference configuration interaction calculations with SOC account are used to generalize spin-selection rules for the oxygen atmospheric and Herzberg bands in free O 2 molecule and in collision complexes. Intensity enhancement of the atmosphericupon bimolecular collisions are compared with those for Herzberg III transitions A 0 3 D u / X 3 R À g . Electric quadrupole, dipole, and magnetic approximations are used for transition probability calculations. Intensity distribution in rotational lines is also considered. With this background, we propose some simple spin-selection rules for dioxygen activation in enzymatic reactions.

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Section: Analysis Of Intensity Of the Dioxygen Weak Bands In Gas Phasesupporting

confidence: 85%

Section: Analysis Of Intensity Of the Dioxygen Weak Bands In Gas Phasesupporting

confidence: 85%

Dioxygen spectra and bioactivation

Minaev

Murugan

Ågren

2013

Int J of Quantum Chemistry

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“…A key element of response theory is that the usual sum-over-excited-state algorithm is replaced by a set of linear equations that can be performed without prior knowledge of the excited states. 130 This renders the method useful for treating large molecular systems described by approximate wave functions, and molecular properties can calculated analytically. 108,[131][132][133] We note that several other strategies are also available for the computation of phosphorescence phenomenon, such as the variational perturbation theory 134 and spin-orbit coupling configuration interaction (SOC-CI) 135,136 approaches.…”

Section: Response Theory Approachmentioning

confidence: 99%

Behind the scenes of spin-forbidden decay pathways in transition metal complexes

Moitra

Karak

Chakraborty

et al. 2021

Phys. Chem. Chem. Phys.

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“…Theoretical studies of phosphorescence requires an analysis of the excited state electronic structure with account of internal magnetic interactions and vibronic perturbations, the spontaneous emission, and nonradiative quenching channels. The common nonrelativistic Born–Oppenheimer approximation and perturbation theory, and in particular the quadratic response (QR) formalism, − can be used as a starting approach where the phosphorescence acquires dipole activity via spin–orbit coupling (SOC). On that basis, it is readily possible to calculate radiative rate constants and phosphorescence radiative lifetimes − as well as to estimate the role of nonradiative processes under the degradation of the first excited triplet state .…”

Section: Introductionmentioning

confidence: 99%

Theory and Calculation of the Phosphorescence Phenomenon

2017

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Phosphorescence is a phenomenon of delayed luminescence that corresponds to the radiative decay of the molecular triplet state. As a general property of molecules, phosphorescence represents a cornerstone problem of chemical physics due to the spin prohibition of the underlying triplet-singlet emission and because its analysis embraces a deep knowledge of electronic molecular structure. Phosphorescence is the simplest physical process which provides an example of spin-forbidden transformation with a characteristic spin selectivity and magnetic field dependence, being the model also for more complicated chemical reactions and for spin catalysis applications. The bridging of the spin prohibition in phosphorescence is commonly analyzed by perturbation theory, which considers the intensity borrowing from spin-allowed electronic transitions. In this review, we highlight the basic theoretical principles and computational aspects for the estimation of various phosphorescence parameters, like intensity, radiative rate constant, lifetime, polarization, zero-field splitting, and spin sublevel population. Qualitative aspects of the phosphorescence phenomenon are discussed in terms of concepts like structure-activity relationships, donor-acceptor interactions, vibronic activity, and the role of spin-orbit coupling under charge-transfer perturbations. We illustrate the theory and principles of computational phosphorescence by highlighting studies of classical examples like molecular nitrogen and oxygen, benzene, naphthalene and their azaderivatives, porphyrins, as well as by reviewing current research on systems like electrophosphorescent transition metal complexes, nucleobases, and amino acids. We furthermore discuss modern studies of phosphorescence that cover topics of applied relevance, like the design of novel photofunctional materials for organic light-emitting diodes (OLEDs), photovoltaic cells, chemical sensors, and bioimaging.

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Some recent developments of high-order response theory

Cited by 34 publications

References 86 publications

Dioxygen spectra and bioactivation

Dioxygen spectra and bioactivation

Behind the scenes of spin-forbidden decay pathways in transition metal complexes

Theory and Calculation of the Phosphorescence Phenomenon

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