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131.
Martí MP Pino J Boqué R Busto O Guasch J 《Analytical and bioanalytical chemistry》2005,382(2):440-443
The aromatic composition of sugar cane spirits and, in general, of alcoholic beverages, is mainly influenced by the ageing process in wood barrels. There are several factors that affect the quality of the final aged product, but the time of the storage in the barrel is perhaps the most important one. Ageing time must therefore be controlled in order to detect counterfeits; however, this parameter is very difficult to control and, at present, there is no analytical method available to determine it. We propose a quantitative method for determining the ageing time of sugar cane spirits in oak barrels by using an electronic nose based on coupling directly a headspace sampler to a mass spectrometer (HS-MS), and multivariate calibration. The method developed is simple and provides, in 5 min, the ageing time of spirits with an accuracy of about 1 month. 相似文献
132.
Gostev F. E. Petrukhin A. N. Titov A. A. Shienok A. I. Marevtsev V. S. Sarkisov O. M. 《Russian Chemical Bulletin》2003,52(3):557-561
Intramolecular processes in electronic-excited states of 2,4,5-triarylimidazole molecules were studied by femtosecond laser spectroscopy. Experiments were carried out with two types of compounds, namely, those experiencing intramolecular proton transfer and two model compounds in which it is impossible. Schemes of the processes studied were proposed and the characteristic rate constants were determined. The excited-state intramolecular proton transfer (ESIPT) in the molecules with planar structure of the reaction center is a very fast process (100 fs). If the reaction center has a nonplanar structure and, hence, the intramolecular hydrogen bond is weakened, the ESIPT time is determined by the time of conformational rearrangement of the molecule. 相似文献
133.
NH_2基态和激发态的SAC-CI和量子拓扑方法研究郑世钧,蔡新华,宋天乐,孟令鹏,中迁博,波田雅彦(河北师范学院化学系,石家庄,050091)(京都大学工程学院京都,日本)关键词SAC-CI方法,激发态,电子密度,拓扑分析用量子拓扑学方法研究激发态... 相似文献
134.
135.
We present a theoretical study of dissociative photoionization of H2 via the 1Πu symmetry in the photon energy range 30–43 eV. Our results explain the various peaks observed in the experiments below 40 eV and illustrate, in particular, the important role of the 2Πu(2pπu) ionization threshold. At higher photon energies, they suggest the existence of new resonance structures that may be associated with doubly excited states of H2 lying above the third and fourth ionization thresholds (the Q3 and Q4 resonance series). From the calculated resonance parameters, we conclude that the dominant mechanism at high photon energies should involve the Q4 (and probably higher) doubly excited states of H2. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 相似文献
136.
A 285-pomt multi-reference configuration-interaction involving single and double excitations ( MRS DCI) potential energy surface for the electronic ground state of L12H is determined by using 6-311G (2df,2pd)basis set.A Simons-Parr-Finlan polynomial expansion is used to fit the discrete surface with a x2 of 4.64×106 The equn librium geometry occurs at Rc=0.172 nm and,LiHL1=94.10°.The dissociation energy for reaction I2H(2A)→L12(1∑g)+H(2S) is 243.910 kJ/mol,and that for reaction L12H(2A')→HL1(1∑) + L1(2S) is 106.445 kl/mol The inversion barrier height is 50.388 kj/mol.The vibrational energy levels are calculated using the discrete variable representation (DVR) method. 相似文献
137.
Summary The calculation of electronically excited states with the internally contracted multiconfiguration-reference configuration interaction (CMRCI) method is discussed. A straightforward method, in which contracted functions for all states are included in the basis, is shown to be very accurate and stable even in cases of narrow avoided crossings. However, the expense strongly increases with the number of states. A new method is proposed, which employs different contracted basis sets for each state, and in which eigensolutions of the Hamiltonian are found using an approximate projection operator technique. The computational effort for this method scales only linearly with the number of states. The two methods are compared for various applications.Dedicated in honor of Prof. Klaus Ruedenberg 相似文献
138.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
139.
A. A. Hasanein G. M. El-Subruiti G. O. Younes M. H. Srour 《Journal of solution chemistry》2004,33(12):1481-1499
The electronic absorption spectra of 2-aminopyrimidine (compound I), 2-amino-4-methylpyrimidine (compound II), 2-amino-4,6-dimethylpyrimidine (compound III), 2-amino-4,6-dimethoxypyrimidine (compound IV), 4-amino-2,6-dimethylpyrimidine (compound V), and 4,5-diamopyrimidine (compound VI) have been measured in water and in a series of different organic solvents. The solvent effects on the spectra are discussed and the solvent induced spectral shifts are analyzed in terms of different solute–solvent interaction mechanisms, using the multiple linear regression technique. 相似文献
140.
Summary Time-dependent perturbation theory has been applied to calculate the doubly excited triplet statesNsns:3Se,Npnp:3De andNdnd:3Ge (N=2, 3, 4,n=N+1, ... ,5) for He, Li+, Be2+ and B3+. A time-dependent harmonic perturbation causes simulataneous excitation of both the electrons with a change of spin state. The doubly excited energy levels have been identified as the poles of an appropriately constructed linearized variational functional with respect to the driving frequency. In addition to the transition energies, effective quantum numbers of these doubly excited states have been calculated and analytic representations of their wave functions are obtained. These are utilized to estimate the Coulomb repulsion term for these states which checks the consistency of the wave functions. These wave functions may also be used for calculating other physical properties of the systems. 相似文献