Spectroscopy and Photochemistry of Rydberg States of Small Polyatomic Hydride Molecules

Ashfold, Michael N. R.; Langford, Stephen R.

doi:10.1007/0-306-46938-3_2

Cited by 5 publications

(8 citation statements)

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“…Finally, it is also worth mentioning that the electronic spectra of CH 4 and NH 3 molecules have been also interpreted as arising from Rydberg states at the FC region, having the lowest singlet excited state a valence-Rydberg nature. 14,20 No valence excited states have been characterized in these molecules at the ground-state equilibrium geometry. As for the water molecule, an increase of the valence character of the lowest singlet excited state occurs in these hydrides upon stretching of one of the bonds.…”

Section: Discussionmentioning

confidence: 99%

“…18,19 As shall be discussed below, the electronic spectrum of water in the gas phase is currently interpreted as composed either of different Rydberg series or implying excited states with a significant Rydberg character at the ground-state equilibrium geometry ͑see, for instance, Ref. 20 for a more recent review͒. How can this scenario conciliate with our simple knowledge of the electronic structure of the water molecule?…”

Section: Introductionmentioning

confidence: 99%

“…According to the MS-CASPT2 results, both states are located close to the lowest ionization potential of the molecule ͑ϳ12.6 eV͒, 50 where the absorption spectrum is dominated by the 1b 1 → nd transitions. 20 We will finally discuss briefly some aspects about previous theoretical studies on the excited states of water. The most recent and representative results are included in Table IV.…”

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confidence: 99%

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Excited states of the water molecule: Analysis of the valence and Rydberg character

Rubio

Serrano‐Andrés

Merchán

2008

The Journal of Chemical Physics

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The excited states of the water molecule have been analyzed by using the extended quantum-chemical multistate CASPT2 method, namely, MS-CASPT2, in conjunction with large one-electron basis sets of atomic natural orbital type. The study includes 13 singlet and triplet excited states, both valence and 3s-, 3p-, and 3d-members of the Rydberg series converging to the lowest ionization potential and the 3s-and 3p-Rydberg members converging to the second low-lying state of the cation, 1 2 A 1 . The research has been focused on the analysis of the valence or Rydberg character of the low-lying states. The computation of the 1 1 B 1 state of water at different geometries indicates that it has a predominant 3s-Rydberg character at the equilibrium geometry of the molecule but it becomes progressively a valence state described mainly by the one-electron 1b 1 → 4a 1 promotion, as expected from a textbook of general chemistry, upon elongation of the O-H bonds. The described valence-Rydberg mixing is established to be originated by a molecular orbital ͑MO͒ Rydbergization process, as suggested earlier by R. S. Mulliken ͓Acc. Chem. Res. 9, 7 ͑1976͔͒. The same phenomenon occurs also for the 1 1 A 2 state whereas a more complex behavior has been determined for the 2 1 A 1 state, where both MO Rydbergization and configurational mixing take place. Similar conclusions have been obtained for the triplet states of the molecule.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Excited states of the water molecule: Analysis of the valence and Rydberg character

Rubio

Serrano‐Andrés

Merchán

2008

The Journal of Chemical Physics

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“…This increases the computational costs additionally. More details on the inclusion of Rydberg states in simulations can be found in refs − . Especially in such cases, an ML representation of the electronic wave function to reduce the computational time would be highly beneficial.…”

Section: Quantum Chemical Theory and Methodsmentioning

confidence: 99%

Machine Learning for Electronically Excited States of Molecules

2020

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Electronically excited states of molecules are at the heart of photochemistry, photophysics, as well as photobiology and also play a role in material science. Their theoretical description requires highly accurate quantum chemical calculations, which are computationally expensive. In this review, we focus on not only how machine learning is employed to speed up such excited-state simulations but also how this branch of artificial intelligence can be used to advance this exciting research field in all its aspects. Discussed applications of machine learning for excited states include excited-state dynamics simulations, static calculations of absorption spectra, as well as many others. In order to put these studies into context, we discuss the promises and pitfalls of the involved machine learning techniques. Since the latter are mostly based on quantum chemistry calculations, we also provide a short introduction into excited-state electronic structure methods and approaches for nonadiabatic dynamics simulations and describe tricks and problems when using them in machine learning for excited states of molecules.

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“…Velocity mapped ion imaging methods [16,17] are very well suited to such experiments, since subsequent photolysis of the cation necessarily results in formation of a charged photo-product, the recoil velocity (speed and angular) distributions of which are revealed in the image without the need for further experimental influence. The literature contains numerous reports describing aspects of the photochemistry of neutral water molecules [18][19][20], but quantitative photochemical data relating to its cation is much less common -notwithstanding the importance of chemistry involving H 2 O + cations in the upper atmosphere [21], in comet tails [22] and in interstellar clouds [23].…”

Section: Introductionmentioning

confidence: 99%

Velocity map imaging studies of the photodissociation of H₂O⁺cations

et al. 2010

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Spectroscopy and Photochemistry of Rydberg States of Small Polyatomic Hydride Molecules

Cited by 5 publications

References 196 publications

Excited states of the water molecule: Analysis of the valence and Rydberg character

Excited states of the water molecule: Analysis of the valence and Rydberg character

Machine Learning for Electronically Excited States of Molecules

Velocity map imaging studies of the photodissociation of H₂O⁺cations

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Spectroscopy and Photochemistry of Rydberg States of Small Polyatomic Hydride Molecules

Cited by 5 publications

References 196 publications

Excited states of the water molecule: Analysis of the valence and Rydberg character

Excited states of the water molecule: Analysis of the valence and Rydberg character

Machine Learning for Electronically Excited States of Molecules

Velocity map imaging studies of the photodissociation of H2O+cations

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Velocity map imaging studies of the photodissociation of H₂O⁺cations