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1.
Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state 13C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.  相似文献   

2.
A variety of fungal melanins with natural 15N abundance are characterized by solid-state 13C and 15N NMR spectroscopy and are compared to solid-state 13C and 15N NMR spectra of organic matter from representative soils. In all solid-state 15N NMR spectra the peptide/amide region (−220 to −285 ppm) dominates with more than 70% of the total intensity. The region between −285 and −375 ppm, assigned to amino and ammonium groups, always contains more than half of the remaining intensity. The area in the region from −30 to −220 ppm, where aromatic heterocycles would show signals, makes up less than 10% of the total intensity. These findings call into question common structural models for melanins. The solid-state 13C NMR spectra, on the other hand, reveal large differences when the melanins are compared to each other, and to composts and soils. The concentration of the aromatic carbon varies from 5 to 40% in the melanin series. The ratio Caro/Ntot and Cali/Ntot were calculated, and confirm that nitrogen in these samples is bound in Ca-groups rather than in aromatic heterocyclic structures.  相似文献   

3.
任静  李超  刘宇平  武振坤  任磊 《岩矿测试》2018,37(3):275-282
经历反复埋藏暴露演化过程的河流阶地样品,难以用常规方法将原生宇宙核素10Be、26Al有效分离。本文在前人实验方法基础上,使用人工挑选、磁选仪分选及酸洗方法,分离样品中碳酸盐、含铁矿物及大气生成的10Be,进一步优化了石英提纯实验流程。结果表明:长度为9 cm、内径为1 cm的阴离子交换树脂装置匹配4 mol/L氢氟酸淋滤液,可将B、Mg、Ca、Cr、Fe、Mn、Ni、Ti和Be、Al有效分离,Be、Al回收率分别可达95.7%、85.7%。阳离子交换树脂能有效分离Be、Al,两元素回收率均达到85%。获得10Be/9Be和26Al/27Al流程空白分别为2.19×10-15和1.63×10-15。优化后的实验方法显著提高了河流阶地样品中原生宇宙核素10Be、26Al的纯化效率,且10Be/9Be和26Al/27Al流程空白数值与国内外实验室具有可比性。采用本方法获得了成都平原冲积物10Be、26Al暴露年龄分别是76.36±9.51 ka和69.44±14.13 ka,为评价龙门山前缘隐伏断裂构造特征和活动性提供了年代学依据。  相似文献   

4.
Hundreds of samples and 17 variables collected from coalfields of major coal-bearing strata over China except for Tibet and Taiwan, were used in this study. The dry, ash-free basis volatile matter (V r) and caking index (G (RI)) were chosen by means of correlation analysis and stepwise discriminatory analysis as major indices of a new classification. By means of the optimum section, the boundary value of the axis of ordinate (G (RI)) and axis of abscissas (V r) can be determined in the classification system. Thus, aV r –G (RI) classification scheme diagram was formed and bituminous coal was divided into nine classes. Use of correspondence analysis reduced dimensions of sample-expressive space without losing initial information. The trend on the factor surface of samples shows that the classification obtained from correspondence analysis conforms to theV r –G (RI) classification result and further verified the dependability of classification by two indices. At the same time, a certain relationship between the properties of a great variety of coal and their attributes can be explained. Hence, bituminous coal classification becomes more scientific, reasonable, and practical than before.  相似文献   

5.
Immature vitrinite samples from a Miocene lignite seam of western Germany (H/C = 1.14, O/C = 0.41) and alginite concentrates from a Tasmanite deposit of Australia (H/C = 1.60, O/C = 0.10) were pyrolyzed in a stream of argon at heating rates of 0.1 and 2.0°C/min up to temperatures varying from 200 to 670°C. The solid maceral residues were subjected to elemental and microscopical analysis and studied by IR and 13C CP/MAS NMR spectroscopy with respect to structural modifications.The maximum pyrolytic weight loss amounts to 60% of the initial organic matter in the case of vitrinite and to 85% for alginite, the onset of degradation reactions being shifted to higher temperatures with increasing rate of heating. Both infrared and NMR spectra of the vitrinite samples indicate a rapid decomposition of the cellulose component upon heating whereas lignin related structures such as aromatic ether linkages remain remarkably stable. The main hydrocarbon release from vitrinite occurs at very early evolution stages (Tmax = 296°C, Rm = 0.20% at 0.1°C/min; Tmax = 337°C, Rm = 0.23 at 2.0°C/min). Hydrocarbon generation from alginite requires higher temperatures (Tmax = 388 and 438°C) and is completed within a distinctly narrower temperature range.The pronounced increase of vitrinite reflectance between 350 and 670°C seems to be associated with a rather time-consuming reorganization of the residual organic material. The concomitant growth of polyaromatic units is illustrated by the increasing intensity ratio of the aromatic ring stretching vibration bands at 1600 and 1500 cm−1. These reactions are moreover marked by increasing loss of phenolic oxygen and by increasing conversion of aliphatic carbon into fixed aromatic carbon.  相似文献   

6.
Lithospermum (Boraginaceae) belongs to a small group of plant taxa that accumulate biogenic carbonate in their fruits. In this genus, carbonate incrustations form in the cells of the epidermis and sclerenchyma of the pericarp. Fossil Lithospermum fruits (nutlets) with well-preserved calcified tissues commonly occur in Quaternary sediments and cultural layers. We tested the suitability of biogenic carbonate of Lithospermum fruits for radiocarbon dating using a total of 15 AMS measurement results from four modern and 11 fossil samples. The 14C data from modern samples suggest that Lithospermum utilises only atmospheric carbon to synthesise calcite in the nutlets. In general, the ages determined through 14C dating of fossil fruitscorresponded well with the absolute-age intervals for archaeological sites over the last 5000 yr. Biogenic carbonate of Lithospermum fruits, like that of Celtis, represents a new source of chronological information for late Quaternary studies.  相似文献   

7.
Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state 13C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in 13C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in 13C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and 13C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.  相似文献   

8.
【研究目的】揭示武汉北部新城地表水、地下水的氢氧稳定同位素特征及其相互作用。【研究方法】2019年，采集、测定了降水样7件、河水样6件、水库样14件、民井样98件、泉水样3件和钻孔样11件，并收集到武汉站1986—1998年的监测数据50件，以空间分析和流域分析为基础，氢氧稳定同位素分析为手段。【研究结果】（1）武汉降水氢氧同位素随季节变化，并表现出“降雨效应”明显、“温度效应”不明显的特点；（2）地表水在枯水期受到强烈的蒸散发，表现出一定的“地貌效应”与“干支流效应”的特征；（3）民井、泉和钻孔等地下水均源于大气降水，表现出“含水层埋深效应”与“山区平原效应”的特点；（4）枯水期，界河流域中界河获得了上游水库和地下水的补给，夏家寺水库流域中夏家寺水库得到了地下水补给。【结论】氢氧同位素能显著提高武汉北部新城地表水-地下水相互转换规律的认识。创新点：利用各类水体氢氧同位素组成及空间分布特征，揭示了武汉北部新城降水、地表水和地下水相互转换的规律  相似文献   

9.
New40Ar-39Ar thermochronological results from the Ladakh region in the India-Asia collision zone provide a tectono-thermal evolutionary scenario. The characteristic granodiorite of the Ladakh batholith near Leh yielded a plateau age of 46.3 ± 0.6 Ma (2σ). Biotite from the same rock yielded a plateau age of 44.6 ± 0.3 Ma (2σ). The youngest phase of the Ladakh batholith, the leucogranite near Himya, yielded a cooling pattern with a plateau-like age of ∼ 36 Ma. The plateau age of muscovite from the same rock is 29.8 ±0.2 Ma (2σ). These ages indicate post-collision tectono-thermal activity, which may have been responsible for partial melting within the Ladakh batholith. Two basalt samples from Sumdo Nala have also recorded the post-collision tectono-thermal event, which lasted at least for 8 MY in the suture zone since the collision, whereas in the western part of the Indus Suture, pillow lava of Chiktan showed no effect of this event and yielded an age of emplacement of 128.2 ±2.6 Ma (2σ). The available data indicate that post-collision deformation led to the crustal thickening causing an increase in temperature, which may have caused partial melting at the base of the thickened crust. The high thermal regime propagated away from the suture with time.  相似文献   

10.
Five representative sub-bituminous coals from NE part of India have been analyzed with respect to their distribution of carbon functional groups through 13C solid state NMR experiments. The 13C Cross Polarised/Magic Angle Spinning NMR spectra of the coal samples were recorded at temperatures of 23°C, 50°C and 70°C respectively and the changes on their structures were interpreted. The NMR spectra of low rank coals were found to exhibit varying degrees of fine structures. The aromaticities of the coal were also determined from the C/H ratios of coal. Some changes in the peak positions along with the formation of simple aromatic units were observed on mild heating.  相似文献   

11.
Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither 13C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.  相似文献   

12.
We measured both mass-dependent isotope fractionation of δ88Sr (88Sr/86Sr) and radiogenic isotopic variation of Sr (87Sr/86Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ88Sr and 87Sr/86Sr compositions showed three remarkable characteristics: (1) high radiogenic 87Sr/86Sr values and gradual decrease in the 87Sr/86Sr ratios, (2) anomalously low δ88Sr values at the lower part cap carbonate, and (3) a clear correlation between 87Sr/86Sr and δ88Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high 87Sr/86Sr and lighter δ88Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO2 content caused sudden precipitation of cap carbonate from the surface seawater with high 87Sr/86Sr and lighter δ88Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ88Sr ratios, probably caused gradual decrease of the 87Sr/86Sr ratios of the seawater and deposition of carbonate with normal δ88Sr ratios. The combination of 87Sr/86Sr and δ88Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.  相似文献   

13.
Supergene Mn-oxide deposits are widely distributed in Guangxi, Guangdong, Yunnan, and Hunan Provinces, South China, accounting for 18% of the total Mn reserves in the country. Direct dating of supergene Mn enrichment, however, is lacking. In this paper, we present high-resolution 40Ar/39Ar ages of Mn oxides from the Xinrong Mn deposit, western Guangdong, to place numerical constraints on the timing and duration of supergene Mn enrichment. A total of ten cryptomelane samples, spanning a vertical extent of 67 m, were dated using the 40Ar/39Ar laser incremental heating technique, with seven samples yielding well-defined plateau or pseudo-plateau ages ranging from 23.48 ± 0.91 to 2.06 ± 0.05 Ma (2σ). One sample yields a staircase spectrum that does not reach a plateau; the spectrum, however, indicates the presence of two or more generations of Mn oxides in the sample, whose ages are best estimated at 22.34 ± 0.31 and 10.2 ± 0.86 Ma, respectively. The remaining two samples gave meaningless or uninterpretable results due to significant 39Ar recoil and contamination by old phases. The 40Ar/39Ar data thus reveal a protracted history of weathering and supergene Mn enrichment that started at least in the end of the Oligocene or beginning of Miocene and extending into the latest Pliocene. Staircase-apparent age spectra, resulting from banded or botryoidal samples, yield an average growth rate of Mn oxides at 0.6–0.7 × 10−3 mm kyr−1. The values indicate that a 1-mm grain of Mn oxides may host minerals precipitated during a time span of ca. 1.5 m.y., and accumulation of Mn oxides to form economic deposits under weathering environments may take millions of years. The distribution of weathering ages shows that the oldest Mn oxides occur on the top of the profile, whereas the youngest minerals are found at the bottom, suggesting downward propagation of weathering fronts. However, two samples located at the intermediate depths of the profile yield ages comparable with those occurring at the highest elevations. Such a complexity of age distribution is interpreted in terms of preferential penetration of Mn-rich weathering solutions along more permeable fault zones, or as a result of multi stages of dissolution and re-precipitation of Mn oxides. A synthesis of geochronological and geological data suggests that formation of the Xinrong deposit was a consequence of a combination of favorable lithological, climatic, and structural conditions. Because the climatic and structural conditions are similar among the provinces of South China during the Cenozoic, the geochronological results obtained at Xinrong may also have implications for the timing of supergene Mn enrichment throughout South China.  相似文献   

14.
The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (13C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. 13C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CHxO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (fa), O/C and relative proportions of various carbon types estimated by 13C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.  相似文献   

15.
The aim of this study is to determine the isotopic composition (δ18O and δ2H) of interstitial water in bentonites. The study had been carried out from adsorbed vapour in homoionic bentonites. We have worked with the fraction <20 μm of a bentonite from Serrata de Níjar (Almería, Spain). Homoionic sodium and calcium bentonites were prepared as well as variable quantities of exchangeable Na/Ca (75Ca/25Na; 50Ca/50Na; 25Ca/75Na), by mixing pure sodium and calcium suspensions in the appropriate quantities. To carry out the hydration of the samples, every one of them was previously dried at 300 °C overnight, they were subjected to controlled saturation conditions in an atmosphere of different relative humidity and at a constant temperature of 20 °C, until equilibrium was achieved. The different vapour pressures were: P/Po = 0.05; P/Po = 0.078; P/Po = 0.15; P/Po = 0.32; P/Po = 0.45; P/Po = 0.63; P/Po = 0.8; P/Po = 1, obtained from the saturated solutions of different salts or sulphuric acid.The saturation water was extracted for isotopic analysis from an aliquot of a saturated sample. The technique used was vacuum extraction based on a modification of the one described by Araguás-Araguás et al. (1995).The differentiation between the isotopes of 18O and 2H from interstitial water in the bentonite samples, depending on the different relative humidity, may affect the ions diffusion in the interstitial solutions, since in those from low relative humidities, there could be a higher diffusion velocity as they are formed by molecules of light isotopes, versus interstitial solutions from higher relative humidities or those near saturation. This fact should be taken into account in studies on cation and solute transport from these solutions inside bentonite, even though it is important to continue studying and corroborating it with a larger number of solutions isotopically marked.  相似文献   

16.
We have studied the paleomagnetism of the middle Cretaceous Iritono granite of the Abukuma massif in northeast Japan together with 40Ar–39Ar dating. Paleomagnetic samples were collected from ten sites of the Iritono granite (102 Ma 40Ar–39Ar age) and two sites of its associated gabbroic dikes. The samples were carefully subjected to alternating field and thermal demagnetizations and to rock magnetic analyses. Most of natural remanent magnetizations show mixtures of two components: (1) H component, high coercivity (Bc > 50–90 mT) or high blocking temperature (Tb > 350–560 °C) component and (2) L component, relatively low Bc or low Tb component. H component was obtained from all the 12 sites to give a mean direction of shallow inclination and northwesterly declination (I = 29.9°, D = 311.0°, α95 = 2.7°, N = 12). This direction is different from the geocentric axial dipole field at the present latitude (I = 56.5°) and the typical direction of the Cenozoic remagnetization in northeast Japan. Since rock magnetic properties indicate that the H component of the Iritono granite is carried mainly by magnetite inclusions in plagioclase, this component probably retains a primary one. Thus the shallow inclination indicates that the Abukuma massif was located at a low latitude (16.1 ± 1.6°N) about 100 Ma and then drifted northward by about 20° in latitude. The northwesterly deflection is attributed mostly to the counterclockwise rotation of northeast Japan due to Miocene opening of the Japan Sea. According to this model, the low-pressure and high-temperature (low-P/high-T) metamorphism of the Abukuma massif, which has been well known as a typical location, would have not occurred in the present location. On the other hand, the L component is carried mainly by pyrrhotite and its mean direction shows a moderate inclination and a northwesterly declination (I = 42.8°, D = 311.5°, α95 = 3.3°, N = 9). Since this direction is intermediate between the H component and early Cenozoic remagnetization in northeast Japan, some thermal event would have occurred at lower temperature than pyrrhotite Curie point ( 320 °C) during the middle Cretaceous to early Cenozoic time to have resulted in partial remagnetization.  相似文献   

17.
Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ34S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ34S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in 34S relative to those from the parent coal (average 7.5‰). The δ34S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ34S values for SO4− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.  相似文献   

18.
Two multi-year oxygen isotope (δ18O) records were obtained from archaeological Ostrea angasi shells, confirming the potential of this species to provide valuable environmental records for the late Holocene period in southeastern Australia. High-resolution δ18Oshell samples from the O. angasi clearly display a seasonal variability, offering insight into past climate conditions in a region where such information is presently limited.

The oxygen isotope record in O. angasi reflects a combined temperature–salinity signal. Observations of δ18Oshell data from modern specimens are used as a point of reference to assist in decoupling these two influences, with the two archaeological samples compared with the δ18Oshell profile of four modern O. angasi. Assuming similar paleo- δ18Owater values at the collection sites, data from these archaeological shells present a record of temperatures during the period of their growth that are consistently lower than modern day, with mean annual temperatures ～2°C cooler.  相似文献   


19.
Stratigraphic analysis of alluvial/colluvial sequences and 14C dating have been used as proxies for Holocene climate changes in the highlands of Tigray (northern Ethiopia). The studied records show alternations of buried soils and peaty–clayey sediments, pointing to wet, stabilization phases, and organic-free colluvium layers resulting from the abrupt occurrence of dry-climate episodes. The 14C dates, mostly unpublished, cluster in the 11,090–9915, 9465–9135, 8450–7330, 6720–3635, 2710–2345, and 1265–790 cal yr B.P. time spans. Evidence of subsequent pedogenesis is lacking in the area, apart from a buried humified horizon dated at 300 ± 60 14C yr B.P. (460–295 cal yr B.P.). Both the timing and the pattern of Tigray paleoclimatic events fit the corresponding framework, based on lake level changes, previously implemented for the Main Rift Valley. These findings give further support for arguing that the forcing mechanisms of the wet/dry fluctuations during the Holocene were effective over a large scale.  相似文献   

20.
The behaviour of the ammonium ion in synthetic buddingtonite, N(D,H)4AlSi3O8, has been studied by infrared (IR) spectroscopy from 20 K to 298 K and by 2H NMR spectroscopy from 120 K to 298 K. IR spectra were collected from 500 to 3500 cm–1. Static 2H NMR spectra collected at 298 K and 120 K are very similar, consisting of a single sharp isotropic resonance, indicating complete averaging of quadrupolar interactions and implying that at these temperatures the ammonium ion is in rapid (<1 s) randomised motion within the M-site cavity of the feldspar framework. NMR spectroscopy indicates that the splitting of the internal modes of the ammonium ion observed by IR spectroscopy is not due to freezing in of the ammonium ion. This observation rules out the formation of a preferred N–H...O hydrogen bond, with precession of the ion about it, as proposed by Kimball and Megaw (1978), because any N–H...O hydrogen bond must be very weak and transient in nature. Contraction of the cavity site upon cooling imposes a distortion upon the ammonium ion that affects vibrational modes. This distortion does not affect the motion of the ammonium ion as observed on the NMR time-scale.  相似文献   

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