PH2^+基态及低激发态的构型优化及光谱性质理论研究

本文报道了PH2^+的一组新的ab initio计算结果。给出了PH2^+的基态(X^1A1)及几个低激发态的电子结构和几何构型。这些态的稳定构型都是在MRSD CI水平上优化得到的。在此基础上, 确定了基态到这些低激发态的跃迁能和部分跃迁的振子强度和辐射寿命。     

Electronic states of SnS and SnS+: a configuration interaction study

Ab initio based multireference configuration interaction calculations are carried out for SnS and its monopositive ion using effective core potentials. Potential energy curves and spectroscopic constants of the low-lying states of SnS and SnS+ are computed. The ground-state dissociation energies of the neutral and ionic species are about 4.71 and 2.86 eV, respectively which compare well with the available thermochemical data. The effect of d-electron correlation on the spectroscopic constants of a few low-lying states has been studied. The spin-orbit interaction has also been included to investigate its effect on the spectroscopic properties of both SnS and SnS+. Dipole moment and transition moment curves are also constructed as a function of the bond length. Transition probabilities of some dipole-allowed and spin-forbidden transitions are studied. Radiative lifetimes of a few low-lying states are estimated. The E1sigma+-X1sigma+ transition of SnS is predicted to be the strongest one. The components of the A2sigma(+)(1/2)-X2(2)pi(1/2) transition with parallel and perpendicular polarization are separately analyzed. The vertical ionization energies of the ground-state SnS to the ground and low-lying excited states of the monopositive ion are calculated.     

Structure revision of plakotenin based on computational investigation of transition states and spectroscopic properties

We show that the previously [Tetrahedron Lett.1992, 33, 2579] proposed structure of natural plakotenin must be revised. Recently, the total synthesis of plakotenin was achieved via an intramolecular Diels-Alder reaction from a (E,E,Z,E)-tetraene as linear precursor. Using density functional theory, the computation of the four possible transition states for this reaction shows that the previously proposed structure could only have been formed via an energetically high-lying transition state, which is very unlikely. Instead, we suggest that the structure of plakotenin corresponds to the product formed via the lowest transition state. A comparison of experimental and theoretical optical rotation, circular dichroism, and two-dimensional nuclear Overhauser enhancement spectra conclusively proves that the structure of plakotenin is the one that is suggested by the transition state computations. Moreover, the simulation of the nuclear Overhauser enhancement spectra suggests that it is most likely that the misassignment of the (1)H chemical shifts of two methyl groups has led to the wrong structure prediction in the 1992 work. The previously proposed structure of iso-plakotenin remains unaffected by our structure revision, but the structures of homo- and nor-plakotenin must also be revised. The present work shows how the total synthesis of a natural product, together with the theoretical determination of the barrier heights of the reactions involved, can be of great help to assign its structure. It appears that intramolecular Diels-Alder reactions can be modeled accurately by today's first-principles methods of quantum chemistry.     

Thermal stability and spectroscopic properties of Er3+-doped antimony-borosilicate glasses

This paper reports on the optical spectroscopic properties and thermal stability of Er(3+)-doped antimony-borosilicate glasses for developing 1.5mum optical amplifiers. Upon excitation at 980nm laser diode, an intense 1.5mum infrared fluorescence has been observed with the maximum full width at half maximum (FWHM) of 90nm for Er(3+)-doped antimony-borosilicate glasses. The emission cross-section and the lifetime of the (4)I(13/2) level of Er(3+) ions are 6.3x10(-21)cm(2) and 0.30ms, respectively. It is noted that the product of the emission cross-section and FWHM of the glass studied is as great as 567x10(-21)cm(2)nm, which is comparable or higher than that of bismuthate and tellurite glasses.     

Electronic structure and luminescent properties of Cu+ and Ag+ impurity centers in NaCl

Fluorescence studies of Cu⁺ and Ag⁺ impurity centers embedded in NaCl are reported. The multiple scattering X_α method is used to describe the electronic structure of these ions in NaCl matrix. It is shown that taking into account the external lattice potential is necessary to obtain good results which can be compared to experiment. This has been done through the computation of an embedded NaCl cluster potential. Moreover, in NaCl:Ag⁺, it is also necessary to include relativistic corrections in order to obtain a reliable energy diagram. This is easily done by use of the Wood Hamiltonian, which allows the self-consistent inclusion of Darwin and mass–velocity terms in MS X_α codes. A good quantitative agreement with experiment is finally obtained for the optical excitations and the emission mechanism of the luminescent centers. The metal–chlorine distance is predicted slightly larger than the NaCl bulk value and the harmonic force constant of the a_1g vibrational breathing deformation of the cluster is calculated and found in good agreement within experiment. For the first time the Stoke shift of such systems is evaluated.     

Synthesis and spectroscopic properties of

The title compound has been synthesized as the first oligothiophenophane that has the typical stacking structure of a layered cyclophane and can behave as an ideal pi-dimer model.     

Electronic structures and spectroscopic regularities of phenylene-modified SWCNTs

The equilibrium geometries and electronic structures for a series of single-wall carbon nanotubes (SWCNTs) modified with phenylene were studied using the density functional theory (DFT) at the B3LYP/6-31G(d) level. Of the four configurations of the phenylene-modified SWCNTs, the v-configuration in which the bond is perpendicular to the main axis of the SWCNT is the most thermodynamically stable. The increase in radii of the modified SWCNTs generally leads to a decrease in the energy gaps. The first absorptions in the electronic spectra of the modified SWCNTs compared with those in the electronic spectra of pristine SWCNTs are basically red-shifted. The chemical shifts of bridged carbon atoms connected with phenylene in the v-configuration are shifted downfield relative to those of the pristine SWCNTs. The aromaticity of the rings in SWCNTs is improved owing to the addition of phenylene.     

Electronic states of Mn microclusters

Electronic states of Mn _n ⁺ microclusters forn=4～7 are calculated by the spin-polarized DV-Xα-LCAO method. The energy levels of valence electrons are composed of two parts, the dense levels which contain much 3d electron components and the sparse levels which contain much 4s electron components. The distribution of the 4s electron levels roughly corresponds to that of one-electron orbitals in the shell model. The highest occupied level of the Mn ₅ ⁺ microcluster is located at a 4s electron level, which is filled with electrons, whereas those of the other microclusters are located at partially filled 4s levels or at dense 3d levels. These results explain the origin of the magic numbers observed in Mn cation microclusters.     

Structure and spectroscopic properties of Er3+ doped germanate glass for mid-infrared application

Intense 2.7 μm emission derived from modified Er³⁺ doped germanate glass was reported. Raman spectrum analysis was carried out to grasp glass structure. Based on the absorption spectrum, the Judd–Ofelt parameters and radiative properties were calculated originated from Judd–Ofelt theory. 2.7 μm emission characteristics, stark splitting features and energy transfer processes upon excitation of a conventional 808 nm or 980 nm laser diode were carefully investigated. The prepared glass possesses high spontaneous transition probability (34.28 s⁻¹), large calculated emission cross section (13 × 10⁻²¹ cm²) and gain coefficient (5.4 cm⁻¹) for the ⁴I_11/2 → ⁴I_13/2 transition. These results indicate that Er³⁺ doped germanate glass has potential applications in mid-infrared lasers and amplifiers.     

Theoretical study of spectroscopic and molecular properties of several low‐lying electronic states of CO molecule

The potential energy curves (PECs) of eight low‐lying electronic states (X¹Σ⁺, a³Π, a′³Σ⁺, d³Δ, e³Σ^?, A¹Π, I¹Σ^?, and D¹Δ) of the carbon monoxide molecule have been studied by an ab initio quantum chemical method. The calculations have been performed using the complete active space self‐consistent field method, which is followed by the valence internally contracted multireference configuration interaction (MRCI) approach in combination with the correlation‐consistent aug‐cc‐pV5Z basis set. The effects on the PECs by the core‐valence correlation and relativistic corrections are included. The way to consider the relativistic corrections is to use the third‐order Douglas–Kroll Hamiltonian approximation at the level of a cc‐pV5Z basis set. Core‐valence correlation corrections are performed using the cc‐pCVQZ basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are corrected for size‐extensivity errors by means of the Davidson modification (MRCI+Q). The spectroscopic parameters (D_e, T_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e, α_e, and γ_e) of these electronic states are calculated using these PECs. The spectroscopic parameters are compared with those reported in the literature. Using the Breit–Pauli operator, the spin–orbit coupling effect on the spectroscopic parameters is discussed for the a³Π electronic state. With the PECs obtained by the MRCI+Q/aug‐cc‐pV5Z+CV+DK calculations, the complete vibrational states of each electronic state have been determined. The vibrational manifolds have been calculated for each vibrational state of each electronic state. The vibrational level G(ν), inertial rotation constant B_ν, and centrifugal distortion constant D_ν of the first 20 vibrational states when the rotational quantum number J equals zero are reported and compared with the experimental data. Comparison with the measurements demonstrates that the present spectroscopic parameters and molecular constants determined by the MRCI+Q/aug‐cc‐pV5Z+CV+DK calculations are both reliable and accurate. © 2012 Wiley Periodicals, Inc.     

Mixed and partial oxidation states. Photoelectron spectroscopic evidence

X-ray photoelectron spectra of the single valence platinum complexes K₂[Pt(CN)₄] · 3H₂O(1),K₂[Pt(CN)₄]Cl_0.3 · n H₂O(2) and K₂[Pt(CN)₄]Cl₂ · 3H₂O(3) and the mixed valence compound [Pt^II(C₂H₅NH₂)₄]Cl₄ · [Pt^IV (C₂H₅NH₂)₄Cl₂] · 4H₂O(4) have been measured. It is found that one can distinguish clearly between mixed and single valence compounds by electron spectroscopy. The Pt spectrum of (4) is a superposition of a Pt^II and Pt_IV spectrum. The chemical shift between (1) and (3) is normal, however (2) shows an anomalous low binding energy for the Pt 4f electrons. The importance of using reliable reference peaks for obtaining absolute binding energies is emphasized.     

Synthesis and spectroscopic properties of N-azolylpropanamides

Fourteen N-azolylpropanamides have been prepared by Michael addition of azoles on acrylamide. The compounds have been fully characterized by IR and by ¹H and ¹³C-nmr. The isolated compounds are the most stable derivatives; kinetic compounds were observed but could not be isolated.     

Electronic states of di-t-butylpolyacetylene radical cations

The π-ionization energies of the di-t-butylpolyacetylenes with two, three, four and five conjugated triple bonds have been determined by He (Iα) photoelectron spectroscopy. The assignment of the bands to the Π-states of the corresponding radical cations follows from simple correlations in agreement with previous experience. The influence of the t-butyl groups on the ionization energies is rationalized in terms of traditional, qualitative arguments assuming an inductive and/or hyperconjugative mechanism. However, a more careful analysis shows that the ‘The -higher-the-ionization-energy-the-higher-the-alkyl-induced-shift’ rule is not always true.     

Electronic states of ketene radical cation

The doublet electronic states of ketene, and ketene-d₂, radical cations produced by photoionisation with Helα (58.4 nm) and Hellα (30.4 nm) radiation, were studied by photoelectron spectroscopy. Seven such states were found below 28 eV ionisation energy and were assigned by comparison with the ionisation energies calculated by the correlated PNO-CEPA approach. The agreement is within ≈ 0.3 eV of the experimental data. An analysis of the contributions of reorganisation and correlation effects to the calculated ionisation energies is presented. The vibrational frequencies exciteα in four of the states of ketene-d₂ and ketene are presented and discussed in view of the assignments.     

Electronic states of general mixed crystals

Up to now molecular-orbital calculations of the electronic states of linear mixed crystals have been concerned only with binary systems such as AB, AB₂, and A₂B₂. The purpose of the present treatment is to extend this work to crystals whose elementary cells contain any number of different atoms in any ordered sequence. The formulation of this general theory is based on the resolvent method. Although the approach enables the general properties of delocalized and localized states to be discussed, the more simple cases already solved in the literature can still be easily derived from the general equations. Furthermore, the classification of Tamm and Shockley states retains its significance, even when other kinds of states can occur and various transitions between the clear cut cases can exist. As in earlier investigations, the chemisorption states are related to surface states and have similar properties. The resolvent method is summarized in the Appendix and its connection with the partition technique is shown.     

Electronic states and radiative transitions in LiAr

Ab initio MRD-CI calculations have been carried out on the ground and the eight lowest excited electronic states of LiAr, correlating with excited Li atom states up to 3d ²D. The ground (X²∑⁺ (2s)) and 2 ²Σ⁺ (2p) electronic states are repulsive while the higher excited states show shallow Rydberg minima. Rates of radiative bound-bound and bound-free transitions have been also calculated.     

Electronic states and spin-orbit splitting of lanthanum dimer

Lanthanum dimer (La(2)) was studied by mass-analyzed threshold ionization (MATI) spectroscopy and a series of multi-configuration ab initio calculations. The MATI spectrum exhibits three band systems originating from ionization of the neutral ground electronic state, and each system shows vibrational frequencies of the neutral molecule and singly charged cation. The three ionization processes are La(2)(+) (a(2)∑(g)(+)) ← La(2) (X(1)∑(g)(+)), La(2)(+) (b(2)Π(3/2, u)) ← La(2) (X(1)∑(g)(+)), and La(2)(+) (b(2)Π(1/2, u)) ← La(2) (X(1)∑(g)(+)), with the ionization energies of 39,046, 40,314, and 40,864 cm(-1), respectively. The vibrational frequency of the X(1)Σ(g)(+) state is 207 cm(-1), and those of the a(2)Σ(g)(+), b(2)Π(3/2, u) and b(2)Π(1/2, u) are 235.7, 242.2, and 240 cm(-1). While X(1)Σ(g)(+) is the ground state of the neutral molecule, a(2)Σ(g (+) and b(2)Π(u) are calculated to be the excited states of the cation. The spin-orbit splitting in the b(2)Π(u) ion is 550 cm(-1). An X(4)Σ(g)(-) state of La(2)(+) was predicted by theory, but not observed by the experiment. The determination of a singlet ground state of La(2) shows that lanthanum behaves differently from scandium and yttrium.     

Electronic energy states of certain sensitizers and dielectrics

Abstract— The electron affinities and ionization potentials of amorphous sulfur, vitreous selenium and several phthalocyanines were measured by Nelson's electron beam retardation method and photoelectric emission, respectively. The electron affinities (A_c) measured were: 4.5 eV for sulfur, 3.4eV for selenium, and approximately 4.3 eV for all the phthalocyanines measured. Photoemission thresholds (I_c) were 7.0 eV for sulfur and 6.0 eV for selenium. Two photoionization thresholds (at about 5.2 and 6.1 eV) were found for both α-copper and α-metal-free phthalocyanine; the former is attributed to impurity levels, the latter to bulk states. In each case, the band gap calculated from I_c and A_c was found to be approximately equal to the optical threshold for photoconductivity.