Thermally stimulated exoelectron emission from solid neon

In spite of the negative electron affinity of Ne atoms, appreciable concentrations of electrons can be trapped in solid neon layers formed by depositing the gas on a cold substrate with concurrent electron irradiation. These are trapped at defect sites, and can be promoted into the conduction band in an annealing experiment. They can then recombine with positive charges producing vacuum ultraviolet "thermoluminescence," but can also be extracted from the solid, and detected as an "exoelectron" current. The thermally stimulated exoelectron emission profiles of the electron current versus temperature reveal two broad features near 7.5 and 10 K. These are shown to correspond to two distributions of electron trapping sites with slightly differing activation energies. For the narrower, higher temperature maximum, an average activation energy of about 23 meV is deduced, in good agreement with predictions based on the theory of electronic defect formation.     

Forbidden electronic transitions of P2 in solid neon

Several forbidden electronic transitions of P₂ in solid neon are examined. All of the six observed electronic states of P₂ are found to be remarkably unshifted and unperturbed by the matrix. While some absorptions exhibit sharp zero-phonon lines, others are characterized by broad, intense phonon sidebands. This is shown to be a consequence of the orbitally forbidden nature of the corresponding transitions.     

Photoemission from matrix-isolated nickel atoms

UV photoelectron spectra from Ni atoms isolated in a xenon matrix at 9 K have been measured for the first time using Hell (40 8 eV). Two peaks have been found at 2.8 and 4.6 eV below E_F, which are interpreted as being due to different d⁸s¹ final states of the Ni ion. including a relaxation shift of 2.0 eV. The existence of atomic Ni species in the matrix has been verified by in situ optical absorption spectra.     

Mid-infrared spectra of methane dispersed in solid neon and argon

We have recorded, in absorption, infrared spectra of samples of methane, CH₄ and CD₄, dispersed at molar fraction 0.0001–0.005 in solid neon, in solid argon and in their equimolar solid mixture in the temperature range 3–21 K and in the spectral domain 5000–500 cm⁻¹ at resolution 0.04–0.2 cm⁻¹. We undertook quantitative fitting of the spectral profiles with components of gaussian and lorentzian shapes. Comparison of our spectra in regions of fundamental modes both ν₃ and ν₄ with published spectra of CH₄ and CD₄ in either crystalline para-dihydrogen or droplets of liquid helium indicates evidence for hindered rotation of CH₄ molecules in Ar but not for rotation of CH₄ or CD₄ in Ne or in a mixture of Ne and Ar. For CD₄ in solid Ar, the evidence for even hindered rotation is ambiguous. We make new assignments of lines to ¹³CH₄ and ¹³CD₄ in their environments in solid Ne and Ar.     

The production and spectroscopy of molecular ions isolated in solid neon

Studies of the molecular spectra of small polyatomic molecular ions are stlll in therr infancy. The availability of survey spectra would facilitate the search for individual vibrational and vibronic bands of gas-phase ion species using sophisticated, highly sensitive laser techniques. Deeectable concentrations not only of simpee ions such as CO⁺ ₂ and H⁺ ₂ but also of dimer cations and anions such as O⁺ ₄ and O^- ₄ have been stabilized in solid neon when the parett molecule is codeposited with a beam of excited neon atoms. The vibrational fundamentals heretofore observed for the simpee ions isolated in solid neon lie very close to the positions of the corresponding gas-phase band centers. Molecular spectroscopic data are not yet available for the gas-phase dimer ions. Therefore, it is difficutt to estimate how closely the neon-matrix vibrational frequencies here reported for a numbrr of dimer ions correspond to the gas-phase band centers. Some guidance is available from comparison of the argon-matrix spectra of small molecules hydrogen-bonded to HF with the gasphaee spectra of theee hydrogen-bonded species [55]. In theee studies, the effect of the argon matrix is to enhance the apparent hydrogen-bond strength; the HF stretching frequency is lowered by 1 to 5% from the gas-phase value, and the absorptions contributed by the flexing of the HF with respect to the other molecule are raised by 5% or more. Since neon matrices are generally less perturbing than argon matrices, the deviation from the gas-phase frequencies shoudd be somewhat less in neon-matrix studies. In the present experiments, only the high frequency stretching fundamentals have been observed, suggesting that matrix shifss shoudd amoutt to less than 3 or 4%. Therefore, matrix isolation studies such as theee promise to provide a valuable new tool for the detection and spectroscopic characterization of small molecular ions and cluster ions.     

Gauche- and trans-n-butane and their IR-induced interconversion in solid neon

Both conformers of n-butane are trapped from the gas phase in solid Ne at 4 K. Broad band infrared irradiation (mainly the CH-stretching region) induces interconversions, the quantum yield for the gauche — trans isomerization being approximately eight times higher than that for the reverse process. The energy difference between the conformers was found to be ?3.05 kJ mol^?1. The vibrational spectra of both conformers are given.     

Photoemission from small organic crystals into gases

Electrons emitted from micron-sized positively charged crystals in relatively dense gases in the presence of a levitating external field can escape recapture. The observed photoemission yield depends on the electron kinetic energy, the gas pressure, the particle size and state of charge, and the magnitude of the external field. Data and a theory are presented to describe the probability of escape. For organic crystals, photoemission due to a binuclear process, can exhibit various light intensity dependences. This may be accomplished by varying the triplet exciton concentration in the crystal. A theory to account for this effect using the concept of excitonic detrapping at recombination centers is presented.     

Photoemission from tin and lead cluster anions

Photoelectrons from mass-identified jet-cooled tin and lead cluster anions (Sn _n ^? , Pb _n ^? ) are detached by ultraviolet laser light (hν=3.68 eV). The photoelectron energy spectra give the detachment energies of ground state cluster anions (electron affinities) as well as excitation energies of neutral clusters in the geometry of the anions. The energy spectra for Sn _n ^? are dominated by flat thresholds with ann-dependence similar to that of other group IV clusters. In contrast, for Pb _n ^? we find pronounced narrow lines close to threshold, generally followed by a 0.3–1.4 eV gap which indicates closed-shell behaviour of Pb _n ^? for nearly alln.     

Spectroscopic and picosedond time-resolved studies of vibrational relaxation in naphthazarine in solid neon

Very extensive vibrationally unrelaxed florescence is observed following dye-laser excitation of single vibronic levels of naphthazarine. The rates and pathways of its vibrational relaxation are examined by means of picosecond emission spectroscopy. Analysis of its vibrational and electronic spectra establishes a C_2v symmetry for free naphthazarine.     

Infrared spectrum of Hg(OH)2 in solid neon and argon

Mercury(II) hydroxide molecules have been prepared upon mercury arc lamp irradiation of Hg, H(2), and O(2) mixtures in solid neon and argon. The strongest three infrared absorptions are identified through isotopic substitution (D(2), HD, (18)O(2), (16)O(18)O) and comparison to frequencies from DFT calculations. The isolated Hg(OH)(2) molecule is stable and has a linear O-Hg-O linkage in a C(2) structure with an 86 degrees dihedral angle. However, in aqueous solution Hg(2+) and 2OH(-) may form an Hg(OH)(2) intermediate, which eliminates water and precipitates solid HgO: The solid Hg(OH)(2) compound is not known.     

Infrared spectroscopy and photochemistry of NCCN+ and CNCN+ trapped in solid neon

When a Ne:NCCN sample is codeposited at 4.3 K with neon atoms that have been excited in a microwave discharge, the infrared and near infrared spectra of the resulting deposit include a prominent peak at 1799.5 cm-1, previously assigned to nu3 of NCCN+, and several new absorptions at higher frequencies which are contributed by combination bands of ground-state NCCN+. The exposure of the deposit to near infrared and red light results in the appearance of two new absorptions which are attributed to CNCN+. The reverse isomerization occurs when the sample is exposed to near ultraviolet radiation, but the two new absorptions are regenerated upon subsequent irradiation with near infrared and red light.     

Infrared spectrum of the novel electron-deficient BH(4) radical in solid neon

Laser-ablated boron reacts with hydrogen on condensation in excess neon to give BH4 radical, BH4- anion, and B2H6 as the major products. Identifications are based on 10B and D substitution, DFT frequency calculations, and comparison to previous spectra. Infrared spectra of BH4 support the C2v structure deduced from previous ESR spectra and theoretical calculations with two normal B-H bonds and two long B-H bonds for this novel electron-deficient radical. NBO analysis suggests that the two long B-H bonds and the H- -H bond are one-electron bonds.     

Theory of excimer vibrational relaxation and U.V. emission in solid neon

A quantitative explanation is provided for the observed UV emission from Ne₂^* molecules in solid neon. An expression involving only known molecular quantities and lattice parameters is given for the rate of vibrational relaxation of an excimer, initially formed in a highly excited level, by interaction with the phonons. This expression is used to show that relaxation cannot proceed to the ground vibrational level of Ne₂^* during the radiative lifetime of the excimer (at the low temperatures at which the experiments are done). The calculation brings out that the vibrational population is concentrated at the n = 3 level when radiation takes place. The lineshape for dissociative UV emission from the n = 3 state of the excimer is computed, and found in very good agreement with experiment.     

Sodium hydride clusters in solid hydrogen and neon: infrared spectra and theoretical calculations

Laser-ablated sodium atom reactions with H2 have been investigated in solid molecular hydrogens and neon. The NaH molecule and (NaH)2,3,4 clusters were identified by IR spectra with isotopic substitution (HD and D2) and comparison to frequencies calculated by density functional theory and the MP2 method. The use of para-hydrogen enriched samples provides evidence for a (H2)nNaH subcomplex surrounded by the solid hydrogen matrix cage. The ionic rhombic (NaH)2 dimer is characterized by strong absorptions at 761.7, 759.1, and 757.0 cm(-1), respectively, in solid neon, para-hydrogen, and normal hydrogen matrices. The cyclic sodium hydride trimer and tetramer clusters are also observed. Although the spontaneous reaction of two Li and H2 to form (LiH)2 occurs on annealing in solid H2, the formation of (NaH)2 requires near uv photoexcitation.     

Infrared spectra of ClCN+, ClNC+, and BrCN+ trapped in solid neon

When a mixture of ClCN or BrCN with a large excess of neon is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid includes prominent absorptions of the uncharged isocyanide, ClNC or BrNC, and of the corresponding cation, ClCN+ or BrCN+. The NC-stretching fundamentals of the isocyanides trapped in solid neon lie close to the positions for their previously reported argon-matrix counterparts. The CN-stretching absorptions of ClCN+ and BrCN+ and the CCl-stretching absorption of ClCN+ appear very close to the gas-phase band centers. Absorptions of two overtones and one combination band of ClCN+ are identified. Reversible photoisomerization of ClCN+ to ClNC+ occurs. The two stretching vibrational fundamentals and several infrared and near infrared absorptions associated with electronic transitions of ClNC+ are observed. Minor infrared peaks are attributed to the vibrational fundamental absorptions of the CX and CX(+) species (X=Cl,Br).     

Infrared absorptions of NH3(H2) complexes trapped in solid neon

When a very small concentration of H2 is added to a Ne:NH3=800:1 sample and the resulting mixture is deposited at 4.3 K, a new absorption appears at 4151.1 cm(-1) which can be assigned to the H2 stretching fundamental of H2 (j=1) complexed with NH3. Other new absorptions which appear near the vibrational fundamentals of NH3 are assigned to the NH3 moiety in this complex and in the complex of NH3 with H2 (j=0). The results of experiments in which HD or D2 is added to the Ne:NH3 mixture support these assignments. Ab initio and density functional calculations predict the observed infrared activation of the H2-stretching vibration for a structure in which the axis of the H2 molecule is collinear with the threefold axis of the NH3. The dependence of the observed absorption patterns on the concentration of H2 in the sample indicates that complexes of NH3 with two or more H2 molecules also form readily.     

Laser studies of vibrational energy transfer and relaxation of CO trapped in solid neon and argon

The infrared emission of CO trapped in solid Ne and Ar is observed at low temperature. The first vibrational level of ¹²C¹⁶O is excited by a Q-switched frequency doubled CO₂ laser. The emission spectrum consists of several lines arising from upper vibrational levels of ¹²C¹⁶O and also of ¹³C¹⁶O and ¹²C¹⁸O which are present in natural abundance. An interpretation is proposed which is based on the assumption that long range dipole—dipole interaction is the main physical process involved in these experiments. Resonance energy transfer produces an energy migration among ¹²C¹⁶O molecules without any change in vibrational populations. Phonon assisted energy transfer takes place between vibrational levels of the various isotopic species present in the solution. In order to satisfy the resonance condition a phonon is emitted or absorbed whose energy compensates for the energy mismatch between the transitions in each interacting molecule due to isotopic effect and or vibrational anharmonicity. The range of this process is greatly extended by energy migration. At the low phonon bath temperature phonon emission is much more probable than phonon absorption. So a strong excitation of upper vibrational levels with in some cases population inversions is observed.Molecular impurities act as efficient quenching centers even at very low concentration. When highly purified samples are used, the fluorescence decay time is found to be 20.6 ms in Ne and 14.5 ms in Ar and does not significantly depend upon concentration and temperature. It is concluded that radiationless relaxation is unimportant.     

The infrared spectra of BF3+ and BF2OH+ trapped in solid neon

Observations on a Ne:BF(3) = 400:1 mixture into which a trace of normal or isotopically enriched water had been introduced, codeposited at 4.3 K with a beam of neon atoms that had been excited in a microwave discharge, demonstrate that a pair of absorptions at 1662 cm(-1) and 1722 cm(-1) that were previously assigned to the two boron-isotopic species of BF(3)(+) should be reassigned to a BF(2) stretching fundamental of BF(2)OH(+). The OH stretching fundamental of that product was identified for the first time at 3240 cm(-1). The degenerate BF(3) stretching fundamental of (11)BF(3)(+) appears at an unusually high frequency, 1790 cm(-1), consistent with strong pseudo-Jahn-Teller interaction of that ground-state fundamental with the B?(2)E(') electronic state, as predicted by theory. The recent availability of detailed ab initio and density functional calculations of the vibrational fundamentals of BF(2)(-) and BF(3)(-) facilitates assignment of the infrared absorptions of those two products.     

PANI的内光电发射

利用电化学方法在自组装一层对氨基硫醇（PATP）的金电极上制备三种氧化还原态的聚苯胺（PANI）膜，PANI底层比较致密，表面呈山包状，该膜在K3Fe(CN)6/K4Fe(CN)6溶液的循环伏安图表明了部分氧化氮PANI膜具有良好的电子传输性能，从光电流谱得到氧化态PANI的禁带能为1．45eV，首次发现部分氧化态PANI膜的光电流谱遵循Fowler定律（IPCE^1/2-hv呈线性），具有内光电发射的性质，通过Fowler图得出部分氧化态PANI的绝缘母体的禁带宽度为3．33eV，并且证实该绝缘母体为还原态PANI，从Mott-Schottky图昨到部分氧化态和还原态PANI的平带电位都为0．63V(vs,SCE)，提出了和PANI的颗粒金属岛导电模型一致的内光电发射机理来解释部分氧化态PANI的光电化学过程。