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NH3/HCl and ND3/DCl mixtures condensed in 9. A. Famulari, M. Sironi, M. Raimondi, in Quantum 27. R. A. Bachorz, M. Haranczyk, I. Dabowska, J. Rak,
an argon matrix have been reported (28). Their Systems in Chemistry and Physics (Springer, Netherlands, M. Gutowski, J. Chem. Phys. 122, 204304 (2005).
2000), vol. 1, pp. 361–379. 28. A. J. Barnes, T. R. Beech, Z. Mielke, J. Chem. Soc. Faraday
spectra yield (v = 0→1) vibrational transition 10. Z. Latajka, S. Sakai, K. Morokuma, H. Ratajczak, Trans. II 80, 455 (1984).
values of 1371 and 1113 cm−1, respectively, for Chem. Phys. Lett. 110, 464 (1984). 29. M. J. T. Jordan, J. E. Del Bene, J. Am. Chem. Soc. 122,
the N..H/D..Cl stretching modes of the proton- 11. G. Corongiu et al., Int. J. Quant. Chem. 59, 119 (1996). 2101 (2000).
transferred species, NH4+Cl− and ND4+Cl−. Be- 12. S. Y. Reece, J. M. Hodgkiss, J. Stubbe, D. G. Nocera, 30. T. M. Miller, D. G. Leopold, K. K. Murray, W. C. Lineberger,
Philos. Trans. R. Soc. B 361, 1351 (2006). J. Chem. Phys. 85, 2368 (1986).
cause our spacings are extracted from highly 13. D. Radisic et al., J. Am. Chem. Soc. 127, 6443 (2005). 31. R. A. Kendall, T. H. Dunning Jr., R. J. Harrison, J. Chem.
anharmonic parts of the progressions and the 14. J.-Y. Fang, S. Hammes-Schiffer, J. Chem. Phys. 106, 8442 Phys. 96, 6796 (1992).
(0→1) vibrational frequencies are strongly (1997). 32. ChemCraft Version 1.5 (build 276), www.chemcraftprog.org.
15. J. V. Coe, J. T. Snodgrass, C. B. Friedhoff, K. M. McHugh, 33. This material is based in part on work supported by
affected by matrix effects (28, 29), the agreement
K. H. Bowen, J. Chem. Phys. 87, 4302 (1987). National Science Foundation grant CHE-0517337
is satisfactory. The first three calculated spacings 16. MOLPRO, version 2006.1, a package of ab initio programs; (K.H.B.). We also thank the Polish State Committee for
between the energy levels associated with various H. J. Werner et al. (www.molpro.net). Scientific Research (KBN) for support under grants
excitations of the central hydrogen atom are 1718 17. Gaussian 03, Revision C.02; M. J. Frisch et al., Gaussian, DS/8000-4-0026-8 (M.G.) and N204 127 31/2963 (M.H.)
(0 to 1), 1171 (1 to 2), and 1214 (2 to 3) cm−1. Inc., Wallingford CT, 2004. and the U.S. Department of Energy (DOE) Office of
18. P. R. Taylor, Lecture Notes in Quantum Chemistry II,
The latter value of 1214 cm−1 matches very well B. O. Roos, Ed. (Springer-Verlag, Berlin, 1994).
Basic Energy Sciences Chemical Sciences program (M.G.
and G.K.S.). The research of R.A.B. was supported by the
the spacing between the two most prominent 19. We used augmented, polarized, correlation consistent Deutsche Forschungsgemeinschaft (DFG) through the
peaks [1218 cm−1 (0.151 eV)], suggesting that basis sets of double- and triple-zeta quality (31) Center for Functional Nanostructures (CFN, Project No.
the two strongest peaks in the (NH4+Cl−)− spec- supplemented with additional diffuse s and p functions C3.3) and by a grant from the Ministry of Science, Research
centered on the nitrogen atom with exponents chosen to and the Arts of Baden-Württemberg (Az: 7713.14-300).
trum can be assigned as transitions from v″ = 0 describe the excess electron-charge distribution in the M.H. is a holder of an award from the Foundation for
in the anionic complex to v′ = 2 and 3, respec- dipole-bound anion (ClH…NH3)−. Polish Science (FNP). This research was performed in part
tively, in the neutral manifold (v″ denotes vibra- 20. B. C. Garrett, D. G. Truhlar, J. Am. Chem. Soc. 101, 5207 at the Molecular Science Computing Facility in the
1
(2001).
compounds remains relatively undeveloped. Center for Reticular Chemistry at California NanoSystems
5. F.-M. Tao, J. Chem. Phys. 110, 11121 (1999). Often, the products are either known compounds Institute, Department of Chemistry and Biochemistry,
6. R. Cazar, A. Jamka, F.-M. Tao, Chem. Phys. Lett. 287, 549 or ones with condensed extended structures University of California at Los Angeles, 607 East Charles
(1998). E. Young Drive, Los Angeles, CA 90095, USA. 2Department
(1–7). For multicomponent chemical systems, of Chemistry and Biochemistry, Arizona State University,
7. I. Alkorta, I. Rozas, O. Mo, M. Yanez, J. Elguero, J. Phys.
Chem. A 105, 7481 (2001).
such as in the synthesis of porous metal-organic Tempe, AZ 85287, USA.
8. A. Brciz, A. Karpfen, H. Lischka, P. Schuster, Chem. Phys. structures, it would be reasonable to assume *To whom correspondence should be addressed. E-mail:
89, 337 (1984). that the most energetically favored structures rahul@chem.ucla.edu (R.B.); yaghi@chem.ucla.edu (O.M.Y.)
Fig. 1. The ZIF crystals presented and discussed in this paper. Each row has
the nets (blue line and black dot drawings) shown stacked on top of the tiles
representing the subdivision of space (variously colored polyhedral shapes) in
the net labeled with the three-letter net symbol (18), followed by the single-
crystal XRD structures of ZIFs corresponding to each of the nets. The largest
cage in each ZIF is shown with ZnN4 tetrahedra in blue and CoN4 in pink. The
yellow ball is placed in the structure for clarity and to indicate space in the
cage. H atoms have been omitted [IM and IM-type links are shown in ball-and-
stick representation (C, black; N, green; O, red; Cl, pink)].
Fig. 2. Gas adsorption isotherms and CO2 capture properties of ZIFs. (A) The
N2 adsorption isotherms for heterolinked ZIF-68, 69, and 70 at 77 K. P/P0,
relative pressure; STP, standard temperature and pressure. (B) The CO2 and
CO adsorption isotherms for ZIF-69 at 273 K. For (A) and (B), the gas uptake
and release are indicated by solid and open symbols, respectively. (C)
Breakthrough curves of a stream of CO2/CO mixture passed through a sample
of ZIF-68 showing the retention of CO2 in the pores and passage of CO.
Rogue Mantle Helium and Neon This canonical view, however, conflicts
with several critical observations on OIBs.
Nearly every isotopic system involving lithophile
Francis Albarède elements—notably 87Rb-87Sr, 147Sm-143Nd,
176
Lu-176Hf, and 187Re-187Os—indicates that
The canonical model of helium isotope geochemistry describes the lower mantle as the mantle source of MORB and OIB is de-
undegassed, but this view conflicts with evidence of recycled material in the source of ocean
island basalts. Because mantle helium is efficiently extracted by magmatic activity, it cannot 1010 Age of Earth
remain in fertile mantle rocks for long periods of time. Here, I suggest that helium with high diffusion time scale a 2/D (years)
3
He/4He ratios, as well as neon rich in the solar component, diffused early in Earth’s history from
10 8
low-melting-point primordial material into residual refractory “reservoir” rocks, such as dunites. 1300˚C
The difference in 3He/4He ratios of ocean-island and mid-ocean ridge basalts and the preservation
6 MORB 1460˚C
of solar neon are ascribed to the reservoir rocks being stretched and tapped to different 10
extents during melting.
OIB
104
elium-4 is a radiogenic nuclide produced low 3He/ 4He regions could instead signal man-
10 0
regular stable nuclide. The relative abundances being high for undegassed mantle and very low
1 10 100 1000 10,000
of the two isotopes in oceanic basalts there- for residual mantle. diffusion length scale (m)
fore reflect the evolution of the parent/daughter For historical reasons, He isotopic compo-
ratio (U+Th)/He. These three elements are sitions are reported upside down as R/Ratm, where Fig. 1. Relationship between the time and length
strongly incompatible (i.e., excluded from the R denotes the 3He/ 4He ratio and the subscript scales of diffusion in olivine, using the data of
structure of the major silicate materials), but signals the normalization to the atmospheric Shuster et al. (20) at two different temperatures.
one of them (He) is markedly affected by out- ratio. More than 30 years of observations have The two isotopes of He have comparable diffusion
gassing. Helium preferentially partitions not only shown that mid-ocean ridge basalts (MORBs) rates. At a temperature of 1460°C, He and Ne have
into any gas phase present, but also into liquid are characterized by a narrow range of 3He/ 4He the same diffusivity in quartz, which suggests that
He and Ne diffusivity at mantle temperatures in
during melting (1). Contribution from primitive ratios clustering about 8 Ratm, whereas values in
mantle minerals may not be very different. The set
undegassed mantle gives basalts very low 4He/ excess of 20 Ratm are found nearly exclusively
3 of values labeled “Age of Earth” show that over the
He ratios. The canonical model holds that high in ocean-island basalts (OIBs) (3–6). These data geological ages, He and Ne may have moved by
4
He/3He ratios characterize high (U+Th)/He support the idea that MORBs are derived from diffusion over distances in excess of several kilome-
mantle sources, such as the mantle underneath parts of Earth’s mantle that are significantly more ters. Assuming that melting takes place in the up-
mid-ocean ridges, which were degassed during degassed than the source of OIBs (5, 7, 8). If permost 100 km and an upwelling velocity of 10 m
successive melting events. If He is less incom- pushed to the extreme, the assertion that OIBs year –1 beneath OIBs and 10 cm year –1 beneath
patible than both Th and U, however, these are tapping a deep, largely undegassed part of MORBs gives time scales for diffusion; the corre-
the mantle implies that the lower mantle is pris- sponding distances of diffusion relevant to melt
UMR CNRS 5570, Ecole Normale Supérieure et Université de tine and that mantle convection takes place as extraction for MORB and OIB can be read from
Lyon 1, 69007 Lyon, France. E-mail: albarede@ens-lyon.fr separate layers (9, 10). the curve (see text).
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