Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence

Nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties by means of electrical property expansions: Application to HF, CH4, CF4, and SF6

Electrical property derivative expressions are presented for the nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties. For CF4 and SF6, as opposed to HF and CH4, a term that is quadratic in the vibrational anharmonicity (and not previously evaluated for any molecule) makes an important contribution to the static second vibrational hyperpolarizability of CF4 and SF6. A comparison between calculated and experimental values for the difference between the (anisotropic) Kerr effect and electric field induced second-harmonic generation shows that, at the Hartree-Fock level, the nuclear relaxation/infinite frequency approximation gives the correct trend (in the series CH4, CF4, SF6) but is of the order of 50% too small

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn-Sham density functional theory

The performance of the SAOP potential for the calculation of NMR chemical shifts was evaluated. SAOP results show considerable improvement with respect to previous potentials, like VWN or BP86, at least for the carbon, nitrogen, oxygen, and fluorine chemical shifts. Furthermore, a few NMR calculations carried out on third period atoms (S, P, and Cl) improved when using the SAOP potential

Relations among several nuclear and electronic density functional reactivity indexes

A set of connections among several nuclear and electronic indexes of reactivity in the framework of the conceptual Density Functional Theory by using an expansion ofthe energy functional in terms of the total number of electrons and the normal coordinates within a canonical ensemble was derived. The relations obtained provided explicit links between important quantities related to the chemical reactivity of a system. This paper particularly demonstrates that the derivative of the electronic energy with respect to the external potential of a system in its equilibrium geometry was equal to the negative of the nuclear repulsion derivative with respect to the external potential

Hearing screening with otoacoustic emissions in pediatric outpatient facilities : ages birth through five

This paper discusses the use of otoacoustic emissions (OAEs) in performing outpatient hearing screening for children, birth to age five.

A consumer survey designed to identify attitudes, knowledge, acceptance, and use of assistive listening devices in public facilities

This paper presents a consumer survey of hearing-impaired persons used to identify their attitudes, knowledge, acceptance, and use of assistive listening devices in public facilities.

Beyond retrenchment over Iran: can the EU offer a framework for regional security? CEPS Commentary, 3 September 2012

A new and far-reaching round of sanctions imposed recently on Iran by the EU is starting to hurt the country, its economy and its citizens. Yet Iran’s leadership seems deaf to demands for international weapons inspectors to be allowed unhindered access to its nuclear enrichment facilities. With a regime that is not likely to sway to international and domestic pressure, and in view of the shifting strategic landscape in the Middle East, the question is whether the twin-track approach of sanctions and diplomacy should be kept up, or whether it should make way for an alternative set of policies that could preserve the fragile stability in the wider Middle East and turn a vicious circle into a virtuous one. In this new Commentary, CEPS Senior Research Fellow Steven Blockmans argues that the High Representative of the EU for Foreign Affairs and Security Policy, supported by the European External Action Service, is in a good position to offer a negotiated way out of this seemingly intractable situation.