Theoretically designed M@diaza[2.2.2]cryptand complexes: the role of non-covalent interactions in promoting NLO properties of organic electrides.

Organic excess electron compounds with significant nonlinear optical (NLO) properties are widely employed in optoelectronic applications. Herein, single-alkali metals with diaza[2.2.2] cryptand (M@crypt,M=Li, Na, and K) are investigated for optoelectronic and NLO properties by using the density functional theory. Thermodynamic and kinetic stabilities of present complexes are computed through interaction energy (Eint) and ab-initio molecular dynamic (AIMD) simulations. M@crypt complexes carry excess electrons and mimic molecular electrides. Quantum theory of atoms in molecules (QTAIM) analysis and reduced density gradient (RDG) spectra demonstrate the roles of the weak van der Waals (vdW) interactions between metal and complexant. The remarkable hyperpolarizability (ßo) value up to 1.41 × 106 au may be credited to the presence of loosely bound excess electrons. The hyper Rayleigh scattering hyperpolarizability (ßHRS) is recorded up to 1.31 × 106 au for the K@crypt. Furthermore, frequency-dependent first-order and second-order hyperpolarizability is more prominent at the applied frequency of ω = 0.042823 au. The electron localizing function (ELF) and localized orbital locator (LOL) analysis further disclose the nature of interaction between alkali metal and complexant. The TD-DFT method is adopted to get excited state parameters and absorbance properties. An electron density difference map (EDDM) is exploited to evaluate the orbital contributions in excited states. Hence, the studied electride may become a promising candidate for NLO materials. We anticipate that the present work will provide insight into further development of molecular electride for optoelectronic applications.

Organic electrides M@cryptand [2.2.2] (where M=Li, Na, and K) are examined as excess electrons, where vdW forces play important roles in promoting the NLO properties.

Superalkali nature of the Si9M5 (M = Li, Na, and K) Zintl clusters: a theoretical study on electronic structure and dynamic nonlinear optical properties.

Zintl clusters have attracted widespread attention because of their intriguing bonding and unusual physical properties. We explore the Si9 and Si9M5 (where M = Li, Na, and K) Zintl clusters using the density functional theory combined with other methods. The exothermic nature of the Si9M5 cluster formation is disclosed, and the interactions of alkali metals with pristine Si9 are shown to be noncovalent. The reduced density gradient analysis is performed, in which increased van der Waals interactions are observed with the enlargement of the size of alkali metals. The influence of the implicit solvent model is considered, where the hyperpolarizability (ßo) in the solvent is found to be about 83 times larger than that in the gas phase for Si9K5. The frequency-dependent nonlinear optical (NLO) response for the dc-Kerr effect is observed up to 1.3 × 1011 au, indicating an excellent change in refractive index by an externally applied electric field. In addition, natural bonding orbitals obtained from the second-order perturbation analysis show the charge transfer with the donor-acceptor orbitals. Electron localization function and localized orbital locator analyses are also performed to better understand the bonding electrons in designed clusters. The studied Zintl clusters demonstrate the superalkali character in addition to their remarkable optical and nonlinear optical properties.

Soothing the heart with music: A feasibility study of a bedside music therapy intervention for critically ill patients in an urban hospital setting.

OBJECTIVES: Music therapy has been shown to be effective for reducing anxiety and pain in people with a serious illness. Few studies have investigated the feasibility of integrating music therapy into general inpatient care of the seriously ill, including the care of diverse, multiethnic patients. This leaves a deficit in knowledge for intervention planning. This study investigated the feasibility and effectiveness of introducing music therapy for patients on 4 inpatient units in a large urban medical center. Capacitated and incapacitated patients on palliative care, transplantation, medical intensive care, and general medicine units received a single bedside session led by a music therapist. METHODS: A mixed-methods, pre-post design was used to assess clinical indicators and the acceptability and feasibility of the intervention. Multiple regression modeling was used to evaluate the effect of music therapy on anxiety, pain, pulse, and respiratory rate. Process evaluation data and qualitative analysis of observational data recorded by the music therapists were used to assess the feasibility of providing music therapy on the units and patients' interest, receptivity, and satisfaction. RESULTS: Music therapy was delivered to 150 patients over a 6-month period. Controlling for gender, age, and session length, regression modeling showed that patients reported reduced anxiety post-session. Music therapy was found to be an accessible and adaptable intervention, with patients expressing high interest, receptivity, and satisfaction. SIGNIFICANCE OF RESULTS: This study found it feasible and effective to introduce bedside music therapy for seriously ill patients in a large urban medical center. Lessons learned and recommendations for future investigation are discussed.

Telemedicine licensure in the United States: the need for a cooperative regional approach.

The extraordinary successes and refinement of modern telemedicine applications in recent years have been diminished somewhat by the anachronistic licensure laws of the 50 state jurisdictions that limit the practice of medicine to specific state geographic boundaries. This approach is deficient when applied to telemedicine because, with the advent of the Internet and modern technological advances, differences in space and time are rendered nearly meaningless. It is recommended in this paper that the practice of telemedicine be handled differently than the practice of face-to-face medicine, as related to licensure. Although it may be argued persuasively that a national licensure model for telemedicine should be advanced, the political and constitutional hurdles may be too great to overcome. It is therefore recommended that a voluntary, regional geographic approach be instituted by jurisdictions already demonstrating a commonality of interests, such as through the Southern Governors' Association or the Western Governors' Association. The benefits to be derived from this approach would include improving access to healthcare and medical specialists, enhancing the quality and timeliness of care, cutting medical costs by moving information instead of people, securing patients' access to medical records and information, and facilitating commercial export of American telemedicine services.