Electron attachment to molecules in a cluster environment

Low-energy dissociative electron attachment (DEA) to the CF(2)Cl(2) and CF(3)Cl molecules in a water cluster environment is investigated theoretically. Calculations are performed for the water trimer and water hexamer. It is shown that the DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster, and that this cross section grows as the number of water molecules in the cluster increases. This growth is explained by a trapping effect that is due to multiple scattering by water molecules while the electron is trapped in the cluster environment. The trapping increases the resonance lifetime and the negative ion survival probability. This confirms qualitatively existing experiments on electron attachment to the CF(2)Cl(2) molecule placed on the surface of H(2)O ice. The DEA cross sections are shown to be very sensitive to the position of the attaching molecule within the cluster and the orientation of the electron beam relative to the cluster.     

One- and two-photon absorption of three-coordinate compounds with different centers (B,Al,N) and a 2,2'-dipyridylnitrogen functional group

A series of three-coordinate octupolar compounds with varied centers (boron, aluminum, and nitrogen), which exhibit very large effective two-photon absorption cross sections have been theoretically studied. The ground state geometries and electronic structures are obtained using the density functional theory with the B3LYP functional and 6-31G(d) basis set, and the results are comparable to the available experimental determinations. Based on the correct geometrical and electronic structures, the one- and two-photon absorptions are predicted by the ZINDO-SOS method. Among these compounds, the boron (B) and aluminum (Al) centers act as acceptors, while the nitrogen center acts as donor according to the net charge changes during the excitation. It is found that (i) the compounds with boron and aluminum centers show two large two-photon absorption peaks, while the molecule with nitrogen center show only one two-photon absorption peak; (ii) the cross sections of the molecules with B or Al as centers are larger than that of the molecule with nitrogen as center; furthermore, the two-photon absorption cross section of the molecule with Al center is larger than that of the molecule with B center, from this point of view, our theoretical prediction provides for the experiment a good new candidate with large two-photon absorption cross section for further research; (iii) lengthening the conjugation bridge by inserting a benzene ring on the organoborane compounds (forming the investigated molecule B-2) enhances the two-photon absorption cross section, and keeping good transparency at the same time.     

烷烃和胺类分子对电子激发态CH(A~2Δ和B~2Σ~-)自由基猝灭

用266nm激光光解CHBr_3分子产生CH(A,B)态自由基,通过测量CH(A,B→X)自发辐射的时间分辨信号测定室温下(CH_3)_2NH、(C_2H_5)_2NH、(C_2H_5)_3N、n-C_5H_(12)、n-C_6H_(14)和n-C_7H_(16)对CH(A,B,v'=0)的猝灭速率常数.发现猝灭速率常数与猝灭剂烷烃分子中的C-H键数近似成线性关系,但对大的烷烃分子,这种增加逐渐趋缓.用碰撞络合物模型计算胺类分子及烷烃分子与CH形成碰撞络合物时的生成截面,结果表明,在电子激发态CH自由基的猝灭过程中,碰撞对子间的多极相互吸引势和色散力作用势可能起重要作用.     

Two-photon absorption cross sections: an investigation of the accuracy of calculated absolute and relative values

We have studied the basis set and electron correlation effects on the ab initio calculations of two-photon absorption cross sections of water. Various series of correlation consistent basis sets up to triply augmented basis sets of valence pentuple zeta level as well as the popular 6-31G(d) basis set have been employed in combination with several coupled cluster, configuration interaction, and density functional theory methods. We find that it is very difficult to obtain converged values of the cross sections for even a small molecule such as water. Acknowledging these difficulties in obtaining a fully converged cross section for a given state, we also investigated the possibility of determining relative cross sections for a series of organic molecules. However, we did not find consistency between the relative cross sections calculated at the Hartree-Fock level and several coupled-cluster methods using the 6-31G(d) and aug-cc-pVDZ basis sets. However, we could reproduce the relative ordering of the two-photon absorption cross sections of the molecules studied at the Hartree-Fock level.     

Quantum state-resolved collision relaxation of highly vibrationally excited SO2

Collision depopulation cross sections of 13 single, highly vibrationally excited levels with 45,000 cm(-1) energy in the electronic ground state of SO(2) in collision with CO in a supersonic jet have been measured. The measurements for these single highly excited quantum states are conducted through pressure dependence of the decay of the fluorescence quantum beat resulted from their coupling with the rovibronic levels in the optically allowed transitions to the (140), (210), and (132) C(1)B(2) levels. The relaxation cross sections of these highly excited states, each with well-defined energy and symmetry, range from 27 to 187 A(2) with an average of 71 A(2). This average cross section is much larger than the hard sphere cross section of 48 A(2). The relaxation cross section is also found to be larger for the quantum states with a larger matrix element in coupling with the "bright" electronically excited level. Both observations suggest a substantial contribution from long range interactions in collision relaxation of highly excited molecules.     

Polymerization of ethylene molecules chemisorbed on CrOH+ as a model system of chromium-containing catalyst

The reaction process of the production of CrOH(C2H4)2(+) was studied in connection with the ethylene polymerization on a silica-supported chromium oxide catalyst (the Phillips catalyst). Cluster ions CrOH(C2H4)2(+) and CrOH(C4H8)+ were produced by the reactions of CrOH+ with C2H4 (ethylene) and C4H8 (1-butene), respectively, and were allowed to collide with a Xe atom under single collision conditions. The cross section for dissociation of each parent cluster ion was measured as a function of the collision energy (collision-induced dissociation, or CID). It was found that (i) the CID cross section for the production of CrOH+ from CrOH(C2H4)2(+) increases sharply at the threshold energy of 3.16 +/- 0.22 eV and (ii) the CID cross section for the production of CrOH+ and C4H8 from CrOH(C4H8)+ also increases sharply at the threshold energy of 3.26 +/- 0.21 eV. In comparison with the calculations based on a B3LYP hybrid density functional method, it is concluded that two ethylene molecules in CrOH(C2H4)2(+) are polymerized to become 1-butene. The calculation also shows that the dimerization proceeds via CrOH(C2H4)+ (ethylene complex) and CrOH(C2H4)2(+) (ethylene complex), in which the ethylene molecules bind with CrOH+ through a pi-bonding.     

Dipole transitions from excited S states of two-electron systems in time-dependent Hartree-Fock theory

Surface enhanced Raman scattering has been observed for O₂ molecules adsorbed on polydiacetylene single crystals. The spectral dependence of the Raman cross section suggests that the enhancement is due to a well-defined electronic transition of energy 2.39 eV which involves a significant degree of charge transfer from the conjugated polydiacetylene backbone to the O₂ molecule.     

Theoretical study of two-photon absorption properties of a series of ferrocene-based chromophores

The electronic structures, one-photon absorption (OPA), and two-photon absorption (TPA) properties of a series of ferrocene-based chromophores with TCF-type acceptors (TCF = 2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran) have been studied by using the ZINDO-SOS method. The results have revealed that OPA and TPA of ferrocenyl derivatives are affected by the strength of the acceptor, especially the pi-bridge conjugation length. The TPA cross section increases with increasing acceptor strength and pi-bridge conjugation length. The TCF-type acceptor with a phenyl group can lead to a larger TPA cross section. Quadrupole molecules have the largest TPA cross sections (2000-3000 GM), which are about 4 times that of the corresponding dipolar molecules, indicating larger interactions between the top and bottom branches. Finally, the origins of the two-photon excitations for ferrocenyl derivatives are analyzed. The calculations show that ferrocenyl derivatives with TCF-type acceptors (especially quadrupole molecules) are promising candidates for TPA materials.     

A Universal Strategy for Aptamer‐Based Nanopore Sensing through Host–Guest Interactions inside α‐Hemolysin

Nanopore emerged as a powerful single‐molecule technique over the past two decades, and has shown applications in the stochastic sensing and biophysical studies of individual molecules. Here, we report a versatile strategy for nanopore sensing by employing the combination of aptamers and host–guest interactions. An aptamer is first hybridized with a DNA probe which is modified with a ferrocene?cucurbit[7]uril complex. The presence of analytes causes the aptamer–probe duplex to unwind and release the DNA probe which can quantitatively produce signature current events when translocated through an α‐hemolysin nanopore. The integrated use of magnetic beads can further lower the detection limit by approximately two to three orders of magnitude. Because aptamers have shown robust binding affinities with a wide variety of target molecules, our proposed strategy should be universally applicable for sensing different types of analytes with nanopore sensors.     

The catalytic mechanism of CO oxidation in AlAu<Subscript>6</Subscript> clusters determined by density functional theory

We present density functional calculations of O₂ and CO adsorption on an AlAu₆ cluster. It is found that in the AlAu₆ cluster the active sites would be first occupied by coming O₂ rather than CO due to a more negative binding energy of the former. Furthermore, the catalytic mechanisms of CO oxidation in AlAu₆ clusters, which are based on a single CO molecule and double CO molecules, are discussed. This investigation reveals that the reaction of a single CO molecule with the AlAu₆O₂ complex has the lowest activation barrier (0.27 eV), which is 0.51 eV lower than that of the pure Au₆^? cluster. For the AlAu₆O₂(CO)₂ complex, due to the structural distortion of the AlAu₆ cluster, the activation barrier of the determination rate is higher by 0.53 eV than that of the AlAu₆O₂CO complex, which shows that the cooperation effect of the second CO molecule can go against CO oxidation. For the Al@Au₆O₂(CO)₂ complex, the activation barrier of the determination rate is lower by 0.07 eV than the path of one CO molecule, which demonstrates that the cooperation effect of the second CO molecule can prompt CO oxidation.     

Effects of conjugation length, electron donor and acceptor strengths on two-photon absorption cross sections of asymmetric zinc-porphyrin derivatives

Exceptionally large two-photon absorption cross sections at the infrared region have been revealed by time-dependent density functional theory calculations for asymmetric charge-transfer conjugated zinc-porphyrin derivatives. The largest two-photon cross section is found to be more than one order of magnitude larger than for the conventional two-photon active organic molecules. The calculations show that the formation of strong charge-transfer states depends on the length of the conjugation bridge between the zinc-porphyrin core and the electron donor/acceptor. The two-photon absorption cross section can be greatly enhanced by increasing the strengths of the electron donor/acceptor.     

Effects of the structure of the branches on the two-photon absorption properties for the multi-branched molecules with nitrogen (N) as coupling center

In order to investigate the effects of the structure of branches on the TPA properties for multi-branched molecules, the TPA cross section is calculated by using ZINDO/SOS method. The investigated mole- cules have different branches (chomorfores based on stilbene, dithienothiophene and flourene) with nitrogen(N) as coupling center. The results show that the cooperative enhancement in multi-branched molecules depends on the structures of the branches and the structures of branches play an important role in the enhancement of the TPA cross section. The designed molecules with stilbene and dithie- nothiophene as branched possess relatively larger two-photon absorption cross sections.     

Theoretical Studies on the One‐ and Two‐Photon Absorption Properties of Double‐bis(styryl)benzene Derivatives

Two series of bis(styryl)benzene derivatives (BSBD), namely the single‐BSBD and the double‐BSBD, were investigated. The equilibrium geometries and electronic structures were obtained by using the density functional theory B3LYP and 6‐31G basis set. In succession, the one‐ and two‐photon absorption properties of all the molecules were studied theoretically with a ZINDO‐SOS (sum‐over‐states) method in detail. It can be seen that the double‐BSBDs have larger two‐photon absorption (TPA) cross sections in the visible‐IR range than the corresponding single‐BSBDs, demonstrating that increasing the molecular dimension is a very effective method to enhance the values of the TPA cross sections. On the other hand, it can be also noticed that the values of the TPA cross sections are correlative with the ability of donating (accepting) electrons of the terminal substituent groups R [N(CH₃)₂, CH₃, H and CF₃] in these molecules. That is, the intramolecular charge transfer is also a factor for the enhancement of the TPA efficiency. To sum up, the idea of increasing the molecular dimension to enhance the TPA cross section value is a helpful direction to explore better TPA materials for practical applications. And the double‐BSBD molecules are promising TPA materials for the further investigation from the standpoint of the high transparency and the larger TPA cross sections.     

Probing mode and site of substrate water binding to the oxygen-evolving complex in the S2 state of photosystem II by 17O-HYSCORE spectroscopy

In the oxygen-evolving complex (OEC) of photosystem II (PSII) molecular oxygen is formed from two substrate water molecules that are ligated to a mu-oxo bridged cluster containing four Mn ions and one Ca ion (Mn4OxCa cluster; Ox symbolizes the unknown number of mu-oxo bridges; x >or= 5). There is a long-standing enigma as to when, where, and how the two substrate water molecules bind to the Mn4OxCa cluster during the cyclic water-splitting reaction, which involves five distinct redox intermediates (Si-states; i = 0,...,4). To address this question we employed hyperfine sublevel correlation (HYSCORE) spectroscopy on H217O-enriched PSII samples poised in the paramagnetic S2 state. This approach allowed us to resolve the magnetic interaction between one solvent exchangeable 17O that is directly ligated to one or more Mn ions of the Mn4OxCa cluster in the S2 state of PSII. Direct coordination of 17O to Mn is supported by the strong (A approximately 10 MHz) hyperfine coupling. Because these are properties expected from a substrate water molecule, this spectroscopic signature holds the potential for gaining long-sought information about the binding mode and site of one of the two substrate water molecules in the S2 state of PSII.     

Changes of coupling between the electrodes and the molecule under external bias bring negative differential resistance

We report a first-principles study of electrical transport and negative differential resistance (NDR) in a single molecular conductor consisting of a borazine ring sandwiched between two Au(100) electrodes with a finite cross section. The projected density of states (PDOS) and transmission coefficients under various external voltage biases are analyzed, and it suggests that the variation of the coupling between the molecule and the electrodes with external bias leads to NDR. Therefore, we propose that one origin of NDR in molecular devices is caused by the characteristics of both the molecule and the electrodes as well as their cooperation, not necessarily only by the inherent properties of certain species of molecules themselves. The changes of charge state of the molecule have minor effects on NDR in this device because the Mulliken population analysis shows that electron occupation variation on the molecule is very small when different external biases are applied.     

The Role of Guest Molecules in the Self-assembly of Metal—ligand Clusters

Abstract

Understanding the self-assembly of nanoscale metal—ligand clusters is an important research area in supramolecular chemistry, especially, if one wishes to develop a truly predictive design strategy for synthesizing these nanoscale clusters. As the building blocks for forming these clusters have become larger and more complex, spacious clusters have been synthesized which often contain large cavities. These assemblies can house guest molecules which play a previously uncharacterized role in the self-assembly processes. We seek to analyze this role: do these guest molecules act as templates? Are the guest molecules necessary for cluster formation? Does the guest drive cluster assemble by forming a stable host—guest complex with the cluster? Must a truly rational design strategy for forming metal—ligand clusters incorporate the use of templates? The role of guest molecules in the self-assembly of nanoscale coordination clusters is reviewed in this article.     

Energy transfer of highly vibrationally excited biphenyl

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold biphenyl in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer of naphthalene, energy transfer of biphenyl shows more forward scattering, less complex formation, larger cross section for vibrational to translational (V→T) energy transfer, smaller cross section for translational to vibrational and rotational (T→VR) energy transfer, larger total collisional cross section, and more energy transferred from vibration to translation. Significant increase in the large V→T energy transfer probabilities, termed supercollisions, was observed. The difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally cold biphenyl is very similar to the difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally hot naphthalene. The low-frequency vibrational modes with out-of-plane motion and rotationlike wide-angle motion are attributed to make the energy transfer of biphenyl different from that of naphthalene.     

Calculated electronic transitions in sulfuric acid and implications for its photodissociation in the atmosphere

We have calculated electronic transitions for sulfuric acid in the ultraviolet region using a hierarchy of coupled cluster response functions and correlation consistent basis sets. Our calculations indicate that the lowest energy singlet transition occurs at 8.42 eV with an oscillator strength of 0.01. The lowest energy triplet state occurs at 8.24 eV. Thus, the cross section of sulfuric acid in the actinic region is likely to be very small and smaller than the upper limit put on this cross section by previous experimental investigations. We estimate the cross section of sulfuric acid in the atmospherically relevant Lyman-alpha region ( approximately 10.2 eV) to be approximately 6 x 10 (-17) cm (2) molecule (-1), a value approximately 30 times larger than the speculative value used in previous atmospheric simulations. We have calculated the J values for photodissociation of sulfuric acid with absorption of visible, UV, and Lyman-alpha radiation, at altitudes between 30 and 100 km. We find that the dominant photodissociation mechanism of sulfuric acid below 70 km is absorption in the visible region by OH stretching overtone transitions, whereas above 70 km, absorption of Lyman-alpha radiation by high energy Rydberg excited states is the favored mechanism. The low lying electronic transitions of sulfuric acid in the UV region do not contribute significantly to its dissociation at any altitude.     

Neon scattering off Sodium clusters at finite temperatures

We present findings from computer simulations of collisions of neon atomic beams with Na20 atomic clusters at different internal temperatures. A functional form for the double differential cross section is determined, and no simple signature of a phase transition is seen, even though the clusters undergo a melting phase transition in the temperature range investigated (100 K–400 K). However, such experiments can be used effectively to measure the internal cluster temperature.