Electronic structure and time-dependent description of rotational predissociation of LiH

Jasik, Patryk; Sienkiewicz, J. E.; Domsta, Joachim; Henriksen, Niels Engholm

doi:10.1039/c7cp02097j

Cited by 6 publications

(8 citation statements)

References 56 publications

(63 reference statements)

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“…The first excited state involves an excitation of Li to give Li(2p) + H(1s), and 3 1 Σ + is the ionic state, Li(1s) + + H(1s) − . At longer bond lengths, the second excited state recrosses a higher dissociative state . The ionic state thus passes through both neutral states during dissociation.…”

Section: Interatomic Charge Transfermentioning

confidence: 99%

“…At longer bond lengths, the second excited state recrosses a higher dissociative state. 31 The ionic state thus passes through both neutral states during dissociation. Figure 2 shows potential energies and charge differences for these three states as a function of bond length.…”

Section: ■ Interatomic Charge Transfermentioning

confidence: 99%

“…Another example is excited-state charge transfer, which is a characteristic of many photochemical processes. It is thus frequently the subject of experimental and theoretical study. − Many heteronuclear diatomics have well-studied avoided crossings between covalent and ion-pair states, where dramatic changes in the atomic charges are realized as the internuclear separation increases and are evinced by the dipole moment. ,, Molecular complexes may also have charge transfer states if the differences in electron affinity between molecules is sufficiently high. This results in the loss of an electron from the donor molecule into an unoccupied (or partially occupied) orbital of an acceptor molecule, creating an ion pair.…”

Section: Introductionmentioning

confidence: 99%

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A Comparison of Partial Atomic Charges for Electronically Excited States

MacDonell

Patchkovskii

Schuurman

2022

J. Chem. Theory Comput.

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Partial atomic charges are a useful and intuitive concept for understanding molecular properties and chemical reaction mechanisms, showing how changes in molecular geometry can affect the flow of electronic charge within a molecule. However, the use of partial atomic charges remains relatively uncommon in the characterization of excited-state electronic structure. Here, we show how wellestablished partial atomic charge methods perform for interatomic, intermolecular, and interbond electron transfer in electronically excited states. Our results demonstrate the utility of real-space partial atomic charges for interpreting the electronic structures that arise in excited-state processes. Furthermore, we show how this analysis can be used to demonstrate that analogous electronic structures arise near photochemically relevant conical intersection regions for several conjugated polyenes. On the basis of our analysis, we find that charges computed using the iterative Hirshfeld approach provide results which are consistent with chemical intuition and are transferable between homologous molecular systems.

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Section: Interatomic Charge Transfermentioning

confidence: 99%

Section: ■ Interatomic Charge Transfermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Comparison of Partial Atomic Charges for Electronically Excited States

MacDonell

Patchkovskii

Schuurman

2022

J. Chem. Theory Comput.

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“…The lowest a higher dissociative state. 29 The ionic state thus passes through both neutral states during dissociation. Figure 2 shows potential energies and charge differences for these three states as a function of bond length.…”

Section: Interatomic Charge Transfermentioning

confidence: 99%

“…[25][26][27] Many heteronuclear diatomics have well-studied avoided crossings between covalent and ion-pair states, where dramatic changes in the atomic charges are realized as the inter-nuclear separation increases and are evinced by the dipole moment. 25,28,29 Molecular complexes may also have charge transfer states if the differences in electron affinity between molecules is sufficiently high. This results in the loss of an electron from the donor molecule into an unoccupied (or partially occupied) orbital of an acceptor molecule, creating an ion pair.…”

Section: Introductionmentioning

confidence: 99%

A comparison of partial atomic charges for electronically excited states

MacDonell,

Patchkovskii,

Schuurman

2021

Preprint

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Partial atomic charges are a useful and intuitive concept for understanding molecular properties and chemical reaction mechanisms, showing how changes in molecular geometry can affect the flow of electronic charge within a molecule. However, the use of partial atomic charges remains relatively uncommon in the characterization of excitedstate electronic structure. Here we show how well-established partial atomic charge methods perform for interatomic, intermolecular and inter-bond electron transfer in electronically excited states. Our results demonstrate the utility of real-space partial atomic charges for interpreting the electronic structures that arise in excited-state processes. Furthermore, we show how this analysis can be used to demonstrate that analogous electronic structures arise near photochemically relevant conical intersection

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Electronic excited states in deep variational Monte Carlo

et al. 2023

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Obtaining accurate ground and low-lying excited states of electronic systems is crucial in a multitude of important applications. One ab initio method for solving the Schrödinger equation that scales favorably for large systems is variational quantum Monte Carlo (QMC). The recently introduced deep QMC approach uses ansatzes represented by deep neural networks and generates nearly exact ground-state solutions for molecules containing up to a few dozen electrons, with the potential to scale to much larger systems where other highly accurate methods are not feasible. In this paper, we extend one such ansatz (PauliNet) to compute electronic excited states. We demonstrate our method on various small atoms and molecules and consistently achieve high accuracy for low-lying states. To highlight the method’s potential, we compute the first excited state of the much larger benzene molecule, as well as the conical intersection of ethylene, with PauliNet matching results of more expensive high-level methods.

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Electronic structure and time-dependent description of rotational predissociation of LiH

Cited by 6 publications

References 56 publications

A Comparison of Partial Atomic Charges for Electronically Excited States

A Comparison of Partial Atomic Charges for Electronically Excited States

A comparison of partial atomic charges for electronically excited states

Electronic excited states in deep variational Monte Carlo

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