共查询到14条相似文献,搜索用时 15 毫秒
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Empirical model potentials are found to be very useful for generating most competitive minima of large water clusters, whereas correlated (e.g. second order-Møller–Plesset perturbation (MP2) theory or higher) calculations are necessary for predicting their accurate energetics and vibrational features. The present study reports the structures and energetics of (H2O)32 clusters at MP2 level using aug-cc-pvDZ basis set, starting with low-lying structures generated from model potentials. Such high-end and accurate calculations are made feasible by the cost-effective fragment-based molecular tailoring approach (MTA) in conjunction with the grafting procedure. The latter is found to yield electronic energies with a sub-millihartree accuracy with reference to their full calculation counterparts. The vibrational spectra of nine low-lying (H2O)32 isomers are obtained from the corresponding MTA-based Hessian matrix. All these low-lying isomers show almost similar spectral features, which are in fair agreement with the experiment. The experimental spectrum of (H2O)32 is thus better understood from the vibrational features of this set of very closely spaced isomers. The present case study of (H2O)32 clearly demonstrates the efficacy in obtaining accurate structures, energetics and spectra at correlated level of theory by combining model potential-based structures with fragmentation methods. 相似文献
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Structural and electronic properties of Bin (n = 2-14) clusters from density-functional calculations
J. M. Jia G. B. Chen D. N. Shi B. L. Wang 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2008,47(3):359-365
The structural and electronic properties of Bin
(n = 2-14) clusters have been systematically studied using gradient-corrected
density-functional theory. For each cluster size, a number of structural
isomers were constructed and optimized to search for the lowest-energy
structure. The competition of several structural patterns such as cages,
superclusters, and layered structures leads to the alternating appearance of
these configurations as global minima. Although the tendency of Bi to form
puckered-layer structures is already well-known, the electronic states of
Bin clusters are still far from that of the bulk. As well, a remarkable
even-odd atom number oscillation is observed in the structural and
electronic properties of the clusters, implying that the stability of
Bin clusters is mainly dominated by the electron shell effect rather
than by geometrical packing. The theoretically calculated values for
electron affinities agree well with available experimental data. 相似文献
4.
E. M. Fernández G. Borstel J. M. Soler L. C. Balbás 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):245-248
The ionic and electronic structure of
(Al2O3)n(Ox)
clusters with n
16 and x
= 0,
1, 2 is studied by means of first principles density functional
calculations, norm-conserving pseudopotentials and a numerical
atomic basis set. The equilibrium geometries have been
determined by total energy minimization, starting with several
initial geometries for each cluster size. The trends obtained
for the atomic arrangements (structural isomers, coordination
numbers, disordered versus
ordered structures, etc.) and the electronic properties
(binding energies, Homo-Lumo gap and dipole moments) are
discussed. For most of the oxidized clusters studied here we
find that the Homo-Lumo gap and the magnitude of dipole moment
of isomeric species can vary drastically. 相似文献
5.
姚建刚 《原子与分子物理学报》2017,34(6)
运用密度泛函理论,对H2O在Yn (n=2-8) 团簇表面的分子吸附与解离吸附两种模式进行了结构优化,电子性质分析。结果表明:分子吸附中H2O倾向于O端吸附于Y-Y原子桥位,而解离吸附中H2O解离的H, O原子倾向于吸附于Yn团簇的面位。两种吸附模式都导致了(解离吸附n=4, 5除外)主团簇Y原子平均键长增大。分子吸附和解离吸附的吸附强度和化学活性都随尺寸增加而增大。解离吸附中体系的稳定性明显高于分子吸附,且与体系的电子壳层效应密切相关。 相似文献
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姚建刚 《原子与分子物理学报》2016,33(4):703-710
运用密度泛函理论,对H2O在Yn (n=2-8) 团簇表面的分子吸附与解离吸附两种模式进行了结构优化,电子性质分析。结果表明:分子吸附中H2O倾向于O端吸附于Y-Y原子桥位,而解离吸附中H2O解离的H, O原子倾向于吸附于Yn团簇的面位。两种吸附模式都导致了(解离吸附n=4, 5除外)主团簇Y原子平均键长增大。分子吸附和解离吸附的吸附强度和化学活性都随尺寸增加而增大。解离吸附中体系的稳定性明显高于分子吸附,且与体系的电子壳层效应密切相关。 相似文献
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Jan Loun Jií ejka Jií Sejkora Jakub Plil Milan Novk Ray L. Frost Sara J. Palmer Eloise C. Keeffe 《Journal of Raman spectroscopy : JRS》2011,42(7):1596-1600
The Raman spectrum of bukovskýite [Fe3+2(OH)(SO4)(AsO4)· 7H2O] has been studied and compared with that of an amorphous gel containing specifically Fe, As and S, which is understood to be an intermediate product in the formation of bukovskýite. The observed bands are assigned to the stretching and bending vibrations of (SO4)2− and (AsO4)3− units, stretching and bending vibrations and vibrational modes of hydrogen‐bonded water molecules, stretching and bending vibrations of hydrogen‐bonded (OH)− ions and Fe3+ (O,OH) units. The approximate range of O H···O hydrogen bond lengths was inferred from the Raman spectra. Raman spectra of crystalline bukovskýite and of the amorphous gel differ in that the bukovskýite spectrum is more complex, the observed bands are sharp and the degenerate bands of (SO4)2− and (AsO4)3− are split and more intense. Lower wavenumbers of δ H2O bending vibrations in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared to those in bukovskýite. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
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利用密度泛函理论,在B3LYP/6-31+G(d, p)基组水平上对苯酚-水团簇C_6H_5OH(H_2O)_n(n=1-6)的可能构型进行全优化,得到了团簇的稳定结构;在B3LYP/6-311++G(d, p)基组水平上计算得到了各团簇构型的总能量和结合能,结果显示,在团簇尺寸较小(n≤5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为平面的环状结构,团簇尺寸较大(n5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为三维立体结构.通过对团簇结合能的二阶差分、最高占据轨道与最低空轨道之间的能隙、费米能级和电离能的分析发现,团簇C_6H_5OH(H_2O)_2的最低能量结构具有较高的稳定性,可能具有幻数结构. 相似文献
10.
Using a first-principles method, we investigate the adsorption and diffusion of a Si adatom on the H-terminated Si(1 1 1) substrate, which would be useful in understanding the initial stages of Si homoepitaxy using a H surfactant. The adatom substitutes H atom(s) to form a monohydride structure or a dihydride structure. In forming the monohydride structure, the energy barrier for H substitution is absent. The adatom migrates on the surface with alternating its chemical state between monohydride and dihydride. These behaviors of the adatom are quite similar to those on the H/Si(0 0 1)2 × 1 surface, despite the significant difference in the substrate structure between both orientations. The resulting diffusion barrier is 1.30 eV, which is also comparable to that on the H/Si(0 0 1)2 × 1 surface. 相似文献
11.
Raman spectroscopy was used to study the mineral bottinoite and a comparison with the Raman spectra of brandholzite was made. An intense sharp Raman band at 618 cm−1 is attributed to the SbO symmetric stretching mode. The low intensity band at 735 cm−1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 501, 516 and 578 cm−1. Four Raman bands observed at 1045, 1080, 1111 and 1163 cm−1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3223, 3228, 3368, 3291, 3458 and 3510 cm−1. The first two Raman bands are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm−1 and two infrared bands at 3434 and 3565 cm−1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O H···O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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本文利用尺寸选择的负离子光电子能谱和理论计算探索Au2Gen-/0 (n=1∽8)团簇的结构演化和电子性质. 通过比较理论模拟谱与实验谱,并使用CCSD(T)理论方法计算异构体的相对能量,从而确定金锗混合团簇的全局最小结构. 本文发现Au2Gen-/0 (n=1∽8)团簇的两个Au原子具有较高的配位数和较弱的亲金相互作用. 负离子团簇和中性团簇的最稳定结构分别处于自旋双重态和自旋单重态. 除了Au2Ge4-/0和Au2Ge5-/0,负离子团簇和中性团簇的全局最小结构具有相似的结构特点. Au2Ge1-/0团簇是一个C2v对称的V形结构,而Au2Ge2-/0团簇是一个C2v对称的双桥连结构. Au2Ge1-负离子团簇是两个Au原子盖帽的Ge4四面体结构,而Au2Ge4中性团簇是两个Au原子盖帽的Ge4菱形结构. Au2Ge5∽8-/0团簇主要采用三棱柱、四棱柱、及五棱柱结构. Au2Ge6是一个C2v对称的四棱柱结构,并表现出σ和π双键性质. 相似文献
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Ray L. Frost Sara J. Palmer Frederick Theiss 《Journal of Raman spectroscopy : JRS》2011,42(5):1163-1167
We have successfully synthesised hydrotalcites (HTs) containing calcium, which are naturally occurring minerals. Insight into the unique structure of HTs has been obtained using a combination of X‐ray diffraction (XRD) as well as infrared and Raman spectroscopies. Calcium‐containing hydrotalcites (Ca‐HTs) of the formula Ca4Al2(CO3)(OH)12·4H2O (2:1 Ca‐HT) to Ca8Al2(CO3)(OH)20· 4H2O (4:1 Ca‐HT) have been successfully synthesised and characterised by XRD and Raman spectroscopy. XRD has shown that 3:1 calcium HTs have the largest interlayer distance. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised Ca‐HTs. The Raman bands observed at around 1086 and 1077 cm−1 were attributed to the ν1 symmetric stretching modes of the (CO32−) units of calcite and carbonate intercalated into the HT interlayer. The corresponding ν3 CO32− antisymmetric stretching modes are found at around 1410 and 1475 cm−1. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
14.
J. Schefer T. Woike M. Imlau B. Delley 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,3(3):349-352
The metastable states of sodiumnitroprusside are extremely stable at temperatures below 200 K. It is possible to allocate structural changes measured by neutron diffraction
to measured spectroscopic parameters, but the amount of the structural change is relatively small for a reaction co-ordinate
as the metastable states have an extremely long lifetime. New hypotheses for related systems try to explain such a phenomena
in two ways: The first way is a bending of the NO-bond in the metastable state, the second one an exchange of the oxygen and nitrogen atoms in the NO-bond
(which can be regarded as an bending). As such changes would be possible also from our density functional calculations, we re-investigated our neutron
diffraction data using the new models. However, our results are not compatible with one of these models. On the contrary,
the neutron diffraction data show partially opposite tendencies. We compare both models with EXAFS measurements, with vibrational
spectroscopic results and the data found by M?ssbauer spectroscopy. We propose a potential scheme for all three states (GS,
and ) extracted from absorption and thermodynamic data to explain the electronic and energetic rearrangement, and the population
dynamics.
Received: 23 June 1997 / Accepted: 13 October 1997 相似文献