Nucleophilicity index based on atomic natural orbitals

A simple method of evaluating a semilocal (regional) nucleophilicity is introduced. The concept involves use of the natural orbitals for atomic populations to identify the most “reactive population” of electrons on particular atom in molecule. The results of test calculations considering the regioselectivity problem in electrophilic aromatic substitution to the benzene derivatives are presented and briefly discussed

Minimal set of molecule-adapted atomic orbitals from maximum overlap criterion

The criterion of maximum overlap with the canonical free-atom orbitals is used to construct a minimal set of molecule-intrinsic orthogonal atomic orbitals that resemble the most their promolecular origins. Partial atomic charges derived from population analysis within representation of such molecule-adopted atomic orbitals are examined on example of first-row hydrides and compared with charges from other methods. The maximum overlap criterion is also utilized to approximate the exact free-atom orbitals obtained from ab initio calculations in any arbitrary basis set and the influence of the resulting fitted canonical atomic orbitals on properties of molecule- adopted atomic orbitals is briefly discussed

On quadratic bond-order decomposition within molecular orbital space

A simple method of analysing and localization of canonical molecular orbitals for particular chemical bond using the MO-resolved bond-order decompo- sition scheme is presented. An alternative definition of classical bond order orbitals is provided and links to communication theory of the chemical bond are outlined and briefly discussed. The introduced procedure of decomposition of quadratic bond orders allows one to analyse two- as well as three- center chemical bonds within the framework of the same theory

Basis set dependence of molecular information channels and their entropic bond descriptors

Information channels from SCFMOcalculations using different basis sets and their entropic bond descriptors are compared within the orbital communication theory. In this information-theoretic (IT) treatment of communications between basis functions the overall covalency and ionicity bond components reflect the average communication noise and information flow, respectively, in the resolution level specified by the adopted set of basis functions. The basis-set dependence of the orbital conditional probabilities and their entropic descriptors of the information covalency/ionicity content is explored. Compared to theminimum set χ of the occupied atomic orbitals of the separated constituent atoms, the extended basis sets of Gaussian orbitals and/or their formal contractions generally give rise to a higher IT-covalency and lower IT-ionicity descriptors of the system chemical bonds. In the augmented set case, χaug. = (χ,ψ), containing the polarization function complement ψ of χ, the use of only χ → χ communications is advocated in a semi-quantitative chemical interpretation of the IT bond indices. The maximum-overlap criterion is used to transform the general (orthonormal) extended basis ξ to its semi-augmented form χ aug. = ξ = ( χ , ψ), in which χ ≈ χ and ψ ≈ ψ,which facilitates the near minimum basis set interpretation of bond descriptors and extraction of communications involving the polarization functions ψ. A similar transformation using the minimum information distance criterion can b

Lunar ore geology and feasibility of ore mineral detection using a far-IR spectrometer

Lunar sulfides and oxides are a significant source of noble and base metals and will be vital for future human colonies' self-sustainability. Sulfide detection (pyrite and troilite) applies to many technological fields and use cases, for example, as a raw material source (available in situ on the Lunar surface) for new solar panel production methods. Ilmenite is the primary iron and titanium ore on the Moon and can provide helium-3 for nuclear fusion and oxygen for rocket fuel. The most important ore minerals have prominent absorption peaks in a narrow far-infrared (FIR) wavelength range of 20-40 $\mu$m, much stronger than the spectral features of other common minerals, including significant silicates, sulfates, and carbonates. Our simulations based on the linear mixing of pyrite with the silicates mentioned above indicated that areas containing at least 10-20% pyrite could be detected from the orbit in the FIR range. MIRORES, Multiplanetary far-IR ORE Spectrometer, proposed here, would operate with a resolution down to <5 m, enabling the detection of areas covered by 2-3 m$^2$ of pyrite (or ilmenite) on a surface of ~17 m$^2$ from an altitude of 50 km, creating possibilities for detecting large and local smaller orebodies along with their stockworks. The use of the Cassegrain optical system achieves this capability. MIRORES will measure radiation in eight narrow bands (0.3 $\mu$m in width) that can include up to five bands centered on the ore mineral absorption bands, for example, 24.3, 24.9, 27.6, 34.2, and 38.8 $\mu$m for pyrite, marcasite, chalcopyrite, ilmenite, and troilite, respectively. The instrument size is 32 $\times$ 32 $\times$ 42 cm, and the mass is <10 kg, which fits the standard microsatellite requirements.Comment: 41 pages, 14 figure

Concept and Design of Martian Far-IR ORE Spectrometer (MIRORES)

Sulfide ores are a major source of noble (Au, Ag, and Pt) and base (Cu, Pb, Zn, Sn, Co, Ni, etc.) metals and will, therefore, be vital for the self-sustainment of future Mars colonies. Martian meteorites are rich in sulfides, which is reflected in recent findings for surface Martian rocks analyzed by the Spirit and Curiosity rovers. However, the only high-resolution (18 m/pixel) infrared (IR) spectrometer orbiting Mars, the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), onboard the Mars Reconnaissance Orbiter (MRO), is not well-suited for detecting sulfides on the Martian surface. Spectral interference with silicates impedes sulfide detection in the 0.4–3.9 μm CRISM range. In contrast, at least three common hydrothermal sulfides on Earth and Mars (pyrite, chalcopyrite, marcasite) have prominent absorption peaks in a narrow far-IR (FIR) wavelength range of 23–28 μm. Identifying the global distribution and chemical composition of sulfide ore deposits would help in choosing useful targets for future Mars exploration missions. Therefore, we have designed a new instrument suitable for measuring sulfides in the FIR range called the Martian far-IR Ore Spectrometer (MIRORES). MIRORES will measure radiation in six narrow bands (~0.3 µm in width), including three bands centered on the sulfide absorption bands (23.2, 24.3 and 27.6 µm), two reference bands (21.5 and 26.1) and one band for clinopyroxene interference (29.0 µm). Focusing on sulfides only will make it possible to adapt the instrument size (32 × 32 × 42 cm) and mass (<10 kg) to common microsatellite requirements. The biggest challenges related to this design are: (1) the small field of view conditioned by the high resolution required for such a study (<20 m/pixel), which, in limited space, can only be achieved by the use of the Cassegrain optical system; and (2) a relatively stable measurement temperature to maintain radiometric accuracy and enable precise calibration

Stationarity of electron distribution in ground-state molecular systems

Stationarity of electron probability distribution within the resolution of atomic orbitals is considered involving some concepts from Orbital Communication Theory and the theory of Markov Processes. A new method of evaluating electron conditional probabilities based on natural orbitals is proposed and briefly discussed