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Abstract The mesoscale spectrum describes the distribution of kinetic energy in the Earth's atmosphere between length scales of 10 and 400 km. Since the first observations, the origins of this spectrum have been controversial. At synoptic scales, the spectrum follows a −3 spectral slope, consistent with two‐dimensional turbulence theory, but a shallower −5/3 slope was observed at the shorter mesoscales. The cause of the shallower slope remains obscure, illustrating our lack of understanding. Through a novel coarse‐graining methodology, we are able to present a spatio‐temporal climatology of the spectral slope. We find convection and orography have a shallowing effect and can quantify this using “conditioned spectra.” These are typical spectra for a meteorological condition, obtained by aggregating spectra where the condition holds. This allows the investigation of new relationships, such as that between energy flux and spectral slope. Potential future applications of our methodology include predictability research and model validation.
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Can the Hartree–Fock kinetic energy exceed the exact kinetic energy?
The Hartree–Fock (HF) approximation has been an important tool for quantum-chemical calculations since its earliest appearance in the late 1920s and remains the starting point of most single-reference methods in use today. Intuition suggests that the HF kinetic energy should not exceed the exact kinetic energy; but no proof of this conjecture exists, despite a near century of development. Beginning from a generalized virial theorem derived from scaling considerations, we derive a general expression for the kinetic energy difference that applies to all systems. For any atom or ion, this trivially reduces to the well-known result that the total energy is the negative of the kinetic energy and, since correlation energies are never positive, proves the conjecture in this case. Similar considerations apply to molecules at their equilibrium bond lengths. We use highly precise calculations on Hooke’s atom (two electrons in a parabolic well) to test the conjecture in a nontrivial case and to parameterize the difference between density functional and HF quantities, but find no violations of the conjecture.
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- Award ID(s):
- 2154371
- PAR ID:
- 10396205
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 15
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 154106
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0105684
