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121.
122.
Spin-spin coupling constants (2h)J(F-F), (1)J(F-H), and (1h)J(H-F) have been obtained for cyclic complexes (FH)(n), with n=2-6, from ab initio equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations. Although both the Fermi-contact (FC) term and (2h)J(F-F) increase and become positive as the cluster size increases, the FC term is not a good quantitative approximation to (2h)J(F-F). The paramagnetic spin-orbit (PSO) and spin-dipole (SD) terms which contribute to (2h)J(F-F) appear to be sensitive to the orientation of the hydrogen-bonded pair. However, the large increase in the FC term and (2h)J(F-F) as the size of the cluster increases is due primarily to the reorganization of sigma electron densities in both ground and excited states, and is another manifestation of cooperativity effects in hydrogen-bonded cyclic polymers. The FC term and (1)J(F-H) always increase upon complex formation, but (1)J(F-H) increases only slightly as the size of the cluster increases due to a concurrent decrease in the PSO term. The changes in (1)J(F-H) as a function of polymer size reflect the polarization of electron density away from H and toward F in the ground state, and the electron reorganization which occurs in the excited states which couple to the ground states through the FC and PSO operators. The FC term is a good approximation to (1h)J(H-F), and is always negative, indicating that the hydrogen bonds in the FH clusters are traditional hydrogen bonds. 相似文献
123.
José Elguero Ibon Alkorta Janet E. Del Bene 《Magnetic resonance in chemistry : MRC》2020,58(8):727-732
Equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to determine coupling constants 1J(X–Y) for 65 molecules HmX–YHn, with X,Y ═ 1H, 7Li, 9Be, 11B, 13C, 15N, 17O, 19F, 31P, 33S, and 35Cl. The computed 1J(X–Y) values are in good agreement with available experimental data. The reduced coupling constants 1K(X–Y) have been derived from 1J(X–Y) by removing the dependence on the magnetogyric ratios of X and Y. Patterns are found for the reduced coupling constants on a 1K(X–Y) surface that are related to the positions of X and Y in the periodic table. 相似文献
124.
125.
Di- and tetraphosphines with rigid phenyl-, biphenyl-, and tetraphenylstannane, -silane, and -methane scaffolds, and various substituents R, have been synthesized and immobilized via triethoxysilane-propagated formation of one or two surface-bound phosphonium moieties. The remaining phosphine groups can be coordinated to metal complexes. All the detective work and proof is done by solid-state NMR spectroscopy. 相似文献
126.
Assessing the Impact of a Statewide STEM Investment on K–12, Higher Education,and Business/Community STEM Awareness Over Time
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Toni A. Sondergeld Carla C. Johnson Janet B. Walten 《School science and mathematics》2016,116(2):104-110
Despite monetary and educational investments in science, technology, engineering, and mathematics (STEM) being at record high levels, little attention has been devoted to generating a common understanding of STEM. In addition, working with business, K–12 schools, and/or institutions of higher education to establish a grassroots effort to help community members understand the importance of STEM regarding the future prosperity of the United States in general, and specifically the preparedness of children for careers of now and the future, has been nonexistent. The purpose of our study is to assess the impact of a statewide STEM professional development program implemented for two years on STEM awareness over time among various community stakeholders (i.e., K–12 teachers, higher education faculty, and business members). STEM awareness and beliefs about STEM engagement, resources, student preparation, and careers all improved over time for all groups. However, business members had the greatest growth over time and held significantly higher awareness compared with the other groups in most areas. Our findings suggest that a statewide STEM partnership/network model is a viable option for growing collective impact and sustainability of STEM K–12 education. 相似文献
127.
Mó O Yáñez M Martín Pendás A Del Bene JE Alkorta I Elguero J 《Physical chemistry chemical physics : PCCP》2007,9(30):3970-3977
Substituent effects on iminoboranes XBNH, HBNX and XBNX (X = H, CH3, NH2, OH, F) have been analyzed in the framework of the NBO, AIM and ELF approaches, using B3LYP/6-311++G(d,p) optimized geometries and electron densities. Boron-substituted derivatives, XBNH, are more stable than the corresponding nitrogen-substituted isomers HBNX, with the energy difference increasing as the electron withdrawing character of the substituent increases. The BN linkage is not much affected by N-substitution, but it is significantly altered when the substituent is attached to the boron atom in both XBNH and XBNX series of compounds. Moreover, substituent effects on the structures of iminoboranes are opposite those observed for the corresponding isoelectronic acetylene derivatives. The ELF analysis indicates that electron-withdrawing substituents enhance the localization of electrons in a torus around the CC or the BN axis. As a result, although electron density is depleted at the bcp, the bond does not necessarily become weaker, since density increases around the periphery, a phenomenon named the "hole" effect. The dissimilarities between acetylene and iminoborane derivatives are primarily a consequence of the significant distortion of this torus in the latter, due to the large difference between the electronegativities of B and N, which leads to a large contribution of the X-B=:N-Y resonance structure in some cases. The "hole" effect is reflected in a reasonable correlation between the Laplacian of the electron density at the bcp and the BN bond length. 相似文献
128.
Giuliano BM Ottaviani P Favero LB Caminati W Grabow JU Giardini A Satta M 《Physical chemistry chemical physics : PCCP》2007,9(32):4460-4464
The rotational spectra of normal and O-d species of the two most stable conformers of chiral 1-phenyl-1-propanol, obtained by free jet millimetre-wave absorption spectroscopy reveal that both conformers are stabilized by a O-H[dot dot dot]pi interaction, and have the Calpha-Cbeta-bond oriented nearly perpendicular to the plane of the benzene ring. The methyl group is trans with respect to the phenyl group for the most stable conformer (T), while it is gauche with respect to the phenyl group and entgegen with respect to the hydroxyl group for the second most stable conformer (GE). The energy difference (E(GE)-E(T)) was estimated to be 50(50) cm(-1) from relative intensity measurements. 相似文献
129.
This paper reports on an integrated analytical approach for the noninvasive characterization of Chinese nephrite samples,
encompassing both geological reference specimens and museum objects. Natural variations induced by cationic substitutions,
as well as human-induced alterations such as heating, which both affect color, are the focus of this contribution. Totally
noninvasive methods of analysis were used, including X-ray fluorescence spectroscopy, Raman microspectroscopy, visible reflectance
spectroscopy and X-ray diffraction; moreover, the feasibility of using a portable Raman spectrometer for the in-field identification
of jades has been demonstrated. Fe/Fe+Mg (% p.f.u.) ratios of the jades have been calculated based on hydroxyl stretching
Raman bands, which will provide an important addition to similar data that are being collected at major museums in the Western
and Eastern hemispheres.
相似文献
130.
Andrews KW Schweitzer A Zhao C Holden JM Roseland JM Brandt M Dwyer JT Picciano MF Saldanha LG Fisher KD Yetley E Betz JM Douglass L 《Analytical and bioanalytical chemistry》2007,389(1):231-239
As part of a study initiating the development of an analytically validated Dietary Supplement Ingredient Database (DSID) in
the United States (US), a selection of dietary supplement products were analyzed for their caffeine content. Products sold
as tablets, caplets, or capsules and listing at least one caffeine-containing ingredient (including botanicals such as guarana,
yerba mate, kola nut, and green tea extract) on the label were selected for analysis based on market share information. Two
or three lots of each product were purchased and analyzed using high-pressure liquid chromatography (HPLC). Each analytical
run included one or two National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) and two
products in duplicate. Caffeine intake per serving and per day was calculated using the maximum recommendations on each product
label. Laboratory analysis for 53 products showed product means ranging from 1 to 829 mg caffeine/day. For products with a
label amount for comparison (n = 28), 89% (n = 25) of the products had analytically based caffeine levels/day of between −16% and +16% of the claimed levels. Lot-to-lot
variability (n = 2 or 3) for caffeine in most products (72%) was less than 10%. 相似文献