This paper results from a round table discussion at the CCTC2018 Conference in Changsha City, Hunan, China, in December 2018. It presents a report on the status, prospects, and issues of conceptual density functional theory (CDFT). After a short exposition on the history of CDFT, its fundamentals, philosophy, and successes are highlighted. Then ten issues for reflection on the future of conceptual DFT are formulated and discussed, ending with one or more summarizing statements on the present status of various concepts/principles/practices and proposed directions for future research. The issues include the further analysis of the energy functional, E[N,v], extended to include effects of temperature, solvent, and mechanical forces, basic requirements for physically acceptable response functions as reactivity descriptors, the use of the grand canonical ensemble, the relevance of CDFT for chemical kinetics and thermodynamics, the domain of validity of CDFT-based principles, the combination of CDFT with reaction path calculations, information-theoretic descriptors, and the treatment of excited states and time dependence. The final issue advocates the transition of CDFT from an interpretative to a predictive mode; we believe this is of utmost importance for promoting CDFT as a viable alternative to wave function-based methods for the practicing chemist, a separate issue treated in the final section.

Conceptual density functional theory: status, prospects, issues

We propose a design method to tune the near-field intensities and absorption spectra of a periodic array of plasmonic bowtie nanoantennas (PBNAs) by introducing the hollow cavities inside the metal nanostructures. The numerical method is performed by finite element method that demonstrates the engineered hollow PBNAs can tune the optical spectrum in the range of 400–3000 nm. Simulation results show the hollow number is a key factor for enhancing the cavity plasmon resonance with respect to the hotspot region in PBNAs. The design efforts primarily concentrate on shifting the operation wavelength and enhancing the local fields by manipulating the filling dielectric medium, outline film thickness, and hollow number in PBNAs. Such characteristics indicate that the proposed hollow PBNAs can be a potential candidate for plasmonic enhancers and absorbers in multifunctional opto-electronic biosensors.

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Tunable Optical Performances on a Periodic Array of Plasmonic Bowtie Nanoantennas with Hollow Cavities

The extension of the E = E[N, v] functional for exploring chemical reactivity in a conceptual DFT context to include external electric fields is discussed. Concentrating on the case of a homogeneous field the corresponding response functions are identified and integrated, together with the conventional response functions such as permanent dipole moment and polarizability, in an extended response function tree associated with the E = E[N, v, e] functional. In a case study on the dihalogens F2, Cl2, Br2, I2 the sensitivity of condensed atomic charges (∂q/∂e) is linked to the polarizability of the halogen atoms. The non-integrated (∂ρ(r)/∂e) response function, directly related to the field induced density change, is at the basis of these features. It reveals symmetry breaking for a perpendicular field, not detectable in its atom condensed counterpart, and accounts for the induced dipole moment directly related to the molecular polarizability. The much higher sensitivity of the electronic chemical potential/electronegativity as compared to the chemical hardness is highlighted. The response of the condensed Fukui functions to a parallel electric field increases when going down in the periodic table and is interpreted in terms of the extension of the outer contours in the non-condensed Fukui function. In the case of a perpendicular field the (∂f(r)/∂e) response function hints at stereoselectivity with a preferential side of attack which is not retrieved in its condensed form. In an application the nucleophilic attack on the carbonyl group in H2CO is discussed. Similar to the dihalogens, stereoselectivity is displayed in the Fukui function for nucleophilic attack (f+) in the case of a perpendicular electric field, and opposite to the one that would arise based on the induced density. Disentangling the expression for the evolution of the Fukui function in the presence of an electric field reveals that this difference can be traced back to local differences in the polarization or induced density between the anionic and the neutral system. This difference may be exploited, e.g. for an appropriately substituted H2CO, to generate enantioselectivity.

Extending conceptual DFT to include additional variables: oriented external electric field

One of the most important electrostatic interactions between molecules is most definitely the hydrogen bond. Understanding the basis of this interaction may offer us the insight needed to understand its effect on the macroscopic scale. Hydrogen bonding is for example the reason for anomalous properties in compounds like water and naturally life as we know it. The strength of the bond depends on numerous factors, among them the electronegativity of participating atoms. In this work we calculated the strength of hydrogen bonds between hydrides of the upper-right part of the periodic table (C, N, O, F, P, S, Cl, As, Se, Br) using quantum-chemical methods. The aim was to determine what influences the strength of strong and weak hydrogen bonds in simple hydrides. Various relationships were checked. A relation between the strength of the bond and the electronegativity of the participating atoms was found. We also observed a correlation between the strength of hydrogen bonds and the inter-atomic distances, along with the dependence on the charge transfer on the atom of the donor. We also report characteristic geometries of different dimers.

Hydrogen bonding between hydrides of the upper-right part of the periodic table

We report on a comprehensive study of electron-impact single and multiple ionization of Xeq+ ions (q = 1, 2, ...,25) at energies from the observed thresholds up to 1000 eV. Special emphasis is on indirect processes and their contributions to the net ionization of the parent ion. Although this work is still in progress, it is clear that indirect processes dominate the cross sections. This is demonstrated for the example of single ionization of Xe22+ ions.

Electron-impact ionization of xenon ions

Detailed level-by-level calculations of cross sections and rate coefficients for electron impact direct ionization and excitation-autoionization of AsI-like ions in the 3d
 104s
 24p
 3 (4S3/2) ground state have been performed. The cross sections are presented in the energy range near the threshold for the five ions Mo9+, Xe21+, Pr26+, Dy33+ and W41+. The rate coefficients are given for all the ions from Sr5+ to U59+ in the AsI sequence at the seven electron temperatures (k
 T
 e
 = 0.1E
 I
 ,0.3E
 I
 ,0.5E
 I
 ,0.7E
 I
 ,E
 I
 ,2E
 I
 and 10E
 I
 , where E
 I
 is the first ionization energy). The calculations include the contribution of direct ionization (DI) calculated using the Lotz formula approximation and the contributions of excitation-autoionization (EA) computed in the framework of the Distorted Wave (DW) approximation for the 4s − nl, 3d − nl and 3p − nl resonant inner-shell excitations. The ionization enhancement due to the EA channels is presented as a function of Z along the AsI isoelectronic sequence. The present results show the great importance of the EA processes; an ionization enhancement factor of up to 6.5 is predicted for instance for Dy33+ (Z = 66) at electron temperature of coronal equilibrium maximum abundance.

Moshe Cohen

Papers

Ionization cross sections and rate coefficients for the ground state of AsI-like ions