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11.
Photoelectron spectra are reported for dimethyl carbonate, ethylene carbonate, oxalic acid, dimethyl oxalate and diethyl oxalate. These spectra are discussed on a composite molecule basis using CNDO/s computational data and many of the individual bands are identified. The differential effects of esterification on ionization energies are discussed briefly. 相似文献
12.
Mulliken-Wolfsberg-Helmholz calculations have been performed on ethylene and methyl-substituted ethylenes. The Mulliken assignment (i.e., that the transition between 5–7 eV isR(3s)N in nature) is validated. Spin-orbit coupling calculations indicate that the weakest olefin band at 2700 Å is too intense to be triplet singlet, as is usually assumed. However, behaviour of a predicted low-energyR
*(3s, 2s)N transition agrees well with the characteristics of these weak bands in the absorption spectra of liquid olefins. That these trends are believable is supported by the accuracy with which the computations predict the experimental changes of ionization potential andVN transition energy caused by increased methylation. In particular, it is predicted that the excitation energy of theVN transition should be strongly dependent on molecular geometry — in agreement with experiment. It is suggested, on the basis of intensity calculations, that theR(3s)N transition gains part of its intensity, at least,via vibronic stealing from theVN transition. Computations on cyclic olefins predict the possibility of several low-lying
* transitions; the unusual broadening of theVN transition in these molecules may possibly be associated with this complexity. Computations on methylene cycloalkanes and cycloalkylidene-cycloalkanes reveal that-strain can lead to low-lying
* (valence-shell) transitions. In general, it is found that the 3s atomic orbital can mix appreciably, in both bonding and antibonding combinations, with valence-shell orbitals.
Supported by The United States Air Force and The United States Atomic Energy Commission-Biology Branchvia Grants to the Louisiana State University. 相似文献
Zusammenfassung Mulliken-Wolfsberg-Helmholz-Rechnungen werden für Äthylen und eine Reihe methylsubstituierter Äthylene durchgeführt. Die Mullikenzuordnung [d. h. der Übergang zwischen 5 –7 eV entsprichtR(3s)N] wird daraufhin für zutreffend erklärt. Spin-Bahn-Kopplungs-Berechnungen deuten darauf hin, daß das schwächste Olefinband bei 2700 Å zu intensiv ist, um — wie gewöhnlich angenommen —in Triplett-Singulett-Übergang zu sein. Andererseits stimmt das Verhalten eines energetisch tief liegendenR *(3s, 2s)N-Übergangs gut mit den Charakteristika dieser schwachen Banden im Absorptionsspektrum der flüssigen Olefine überein. Daß diese Interpretation möglich ist, wird auch durch die Genauigkeit unterstützt, mit der eine Berechnung die experimentell gefundene Änderung von Ionisations- undVN-Übergangsenergie bei zunehmender Methylierung ergibt. Insbesondere wird auch vorhergesagt, daß die Anregungsenergie desVN-Übergangs stark von der molekularen Geometrie abhängt — in Übereinstimmung mit dem Experiment. Es wird deshalb auf Grund einer Intensitätsberechnung vorgeschlagen, daß derR(3s)N-Übergang zumindest einen Teil seiner Intensität durch eine Schwingungs-Anleihe vomVN-Übergang gewinnt. Berechnungen für cyclische Olefine weisen auf verschieden niedrig liegende *-Übergänge hin; die ungewöhnliche Verbreitung derVN-Bande bei diesen Molekülen kann möglicherweise damit zusammenhängen. Berechnungen der Methyl-cycloalkane und der Cycloalkylidin-cycloalkane zeigen, daß eine Spannung im-Gerüst zu einem tief liegenden *-(Valenz-) Übergang führen kann. Im allgemeinen zeigt sich, daß 3s-Zustände merklich an Valenzzuständen beteiligt sein können, und zwar sowohl bei bindenden als auch bei lockernden Molekülzuständen.
Résumé Des calculs Mulliken-Wolfsberg-Helmholz ont été effectués sur l'éthylène et sur la série des éthylènes méthyl-substitués. Ces calculs confirment l'assignation de Mulliken: la transition entre 5–7 eV est de natureNR(3s). Des calculs de couplage spin-orbite montrent que la bande oléfinique la plus faible à 2700 Å est trop intense pour être une transition singulet-triplet comme on le suppose généralement. Cependant, le comportement d'une transition théorique de faible énergieNR * (3s, 2s) est en accord avec les caractéristiques de ces faibles bandes dans le spectre d'absorption des oléfines liquides. La vraisemblance de ce point de vue est renforcée par la précision avec laquelle les calculs prédisent l'évolution des potentiels d'ionisation, et des énergies des transitionsNV par méthylation croissante. En particulier, il est prévu que l'énergie d'excitationNV dépend fortement de la géométrie moléculaire ce qui est en accord avec l'expérience. On suggère sur la base de calculs d'intensité que la transitionNR (3s) tire une partie de son intensité au moins par transfert vibronique à partir de la transitionNV. Des calculs sur des oléfines cycliques prédisent la possibilité de plusieurs transitions * de faible énergie; l'élargissement inhabituel de la transitionN V dans ces molécules pourrait provenir de cette situation. Des calculs sur les méthylène-cycloalkanes et les cycloalkylidène cycloalkanes révèlent la possibilité pour une tension de provoquer l'existence de transitions * (couche de valence) de faible énergie. On trouve qu'en général les orbitales atomiques 3s peuvent se mélanger d'une manière appréciable aux orbitales de la couche de valence donnant des combinaisons liantes et antiliantes.
Supported by The United States Air Force and The United States Atomic Energy Commission-Biology Branchvia Grants to the Louisiana State University. 相似文献
13.
S.P. McGlynn 《Journal of Molecular Spectroscopy》1974,49(2):214-225
The absorption and emission spectra of 1- and 2-naphthoic acids and a number of their derivatives have been investigated. The S1, T1, and S0 energy levels of solvent H-bonded monomers and internally H-bonded dimers are affected by the type of H-bonding, by periinteractions, by steric factors provided by substituent groups, and by solvent effects. The excimer fluorescence of 1-naphthoic acid has been detected and is the sole fluorescece of the crystal; it is attributed to a tetrameric sandwich complex of two dimers. The 1-naphthoic acid crystal also exhibits delayed excimer flurescence of a triplet-triplet annihilative type. 相似文献
14.
It has been 20 years since the European Commission adopted the Green Paper on Future Noise Policy in 1996, taking the first comprehensive step towards the development of an EU-wide noise policy. This document envisioned a directive that would harmonise methods for the assessment of environmental noise and the dissemination of information to the public. This led to the establishment of Directive 2002/49/EC in 2002 also known as the Environmental Noise Directive (END). The END called for the development of strategic noise maps and action plans across every EU Member State in five year intervals. Two phases of noise mapping and action planning have now been completed and Member States are about to embark on the third phase of noise mapping, due in 2017. Focussing on results reported to the European Commission, this study summarises the current state of noise mapping, 20 years after the publication of the Green Paper, and identifies critical needs for future noise mapping phases. 相似文献
15.
The generation of nucleophiles from the combination of aryl boronic acids and catalytic amounts of copper salt allows a reactivity distinct from other organometallic species, such as organolithiums or Grignard reagents. Here we examine how the electronic and steric properties of the boronic acid affect the formation of active nucleophiles and their subsequent reactivity with iminium‐type compounds, showing that electron‐rich substrates display reduced reactivity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
16.
L. Klasing Lj. Pasa Tolić H. Spiegl J. V. Knop S. P. McGlynn 《Journal of mathematical chemistry》1991,8(1):179-184
The 5- and 5-conformations of androstane, androstan-3-one, androstan-16-one, androstan-17-one, androstane-3,16-dione and androstane-3,17-dione have been calculated by the SCF MNDO method, using full geometry optimization, in order to assess the dependence of long-range electronic interactions of the carbonyl groups on their location and on the conformation of the steroid ring system. 相似文献
17.
D. Srzi S. Kazazi B. Kralj L. Klasinc J. Marsel H. Güsten S. P. McGlynn 《International journal of mass spectrometry》2003,230(2-3):135
Metal monocation gas-phase reactions with pyrene (Py) have been investigated. Of those cations which bind Py by abstraction of two hydrogen atoms, there are two subgroups of which Nb+ and Ta+ are the most striking and puzzling representatives. The Ta+-like group binds three Py units consecutively, each by expulsion of two hydrogen atoms, whereas the Nb+ group binds four Py units; however, in this latter case, the second Py attachment occurs without the expulsion of any hydrogen. When perdeuterated Py-D10 is used, the Ta+ group behavior is unaffected, but the Nb+ group now exhibits a considerable degree of Py attachment in which no deuterium atoms are lost in the first reaction step. We will attempt to explain this behavior by using the results of reactions of Nb+ and Ta+ with Py in a Fourier transform mass spectrometer (FTMS). 相似文献
18.
Abstract— This paper discusses the possibility of triplet exciton motion and triplet-triplet annihilation in mixed crystal systems in which the hosts are phenylalanine, tyrosine and trypto-phan and in four protein systems. Triplet-triplet annihilation and triplet transfer are observed in certain phenylalanine- and tryptophan-host systems. No evidence of either triplet transfer or energy multiplication is found in tyrosine-host crystal systems or in any protein system. 相似文献
19.
Simon Green Susan McGlynn Deidre Stuart Paul Fahey Jim Pettigrew Peter Clothier 《International Journal of Mathematical Education in Science & Technology》2018,49(4):571-587
The effect of high school study of mathematics on numeracy performance of sports and exercise science (SES) students is not clear. To investigate this further, we tested the numeracy skills of 401 students enrolled in a Bachelor of Health Sciences degree in SES using a multiple-choice survey consisting of four background questions and 39 numeracy test questions. Background questions (5-point scale) focused on highest level of mathematics studied at high school, self-perception of mathematics proficiency, perceived importance of mathematics to SES and likelihood of seeking help with mathematics. Numeracy questions focused on rational number, ratios and rates, basic algebra and graph interpretation. Numeracy performance was based on answers to these questions (1 mark each) and represented by the total score (maximum = 39). Students from first (n = 212), second (n = 78) and third (n = 111) years of the SES degree completed the test. The distribution of numeracy test scores for the entire cohort was negatively skewed with a median (IQR) score of 27(11). We observed statistically significant associations between test scores and the highest level of mathematics studied (P < 0.05), being lowest in students who studied Year 10 Mathematics (20 (9)), intermediate in students who studied Year 12 General Mathematics (26 (8)) and highest in two groups of students who studied higher-level Year 12 Mathematics (31 (9), 31 (6)). There were statistically significant associations between test scores and level of self-perception of mathematics proficiency and also likelihood of seeking help with mathematics (P < 0.05) but not with perceived importance of mathematics to SES. These findings reveal that the level of mathematics studied in high school is a critical factor determining the level of numeracy performance in SES students. 相似文献
20.
The absorption spectra associated with transitions to the lowest-energy s-type Rydberg states of CH3X and CD3X, X = Cl, Br, and I, have been measured and analyzed. The spectra of the bromides and iodides consist, individually, of four electronic origins of s-excitation type. The vibrational frequency of a given normal mode is more or less identical in all four excited states of any one molecule; and the excited state/ground state ratios of the frequencies of any given normal vibrational mode are essentially identical for all four molecules (i.e., for 16 states, four for each of two bromides and two iodides). The spectra of the chlorides are amenable to a number of different vibronic analyses, none of them unique; these analyses are discussed. 相似文献