排序方式: 共有31条查询结果,搜索用时 0 毫秒
11.
Nunes PM Agapito F Costa Cabral BJ Borges dos Santos RM Martinho Simões JA 《The journal of physical chemistry. A》2006,110(15):5130-5134
The gas-phase C-H bond dissociation enthalpy (BDE) in 1,3-cyclopentadiene has been determined by time-resolved photoacoustic calorimetry (TR-PAC) as 358 +/- 7 kJ mol(-1). Theoretical results from ab initio complete basis-set approaches, including the composite CBS-Q and CBS-QB3 procedures, and basis-set extrapolated coupled-cluster calculations (CCSD(T)) are reported. The CCSD(T) prediction for the C-H BDE of 1,3-cyclopentadiene (353.3 kJ mol(-1)) is in good agreement with the TR-PAC result. On the basis of the experimental and the theoretical values obtained, we recommend 355 +/- 8 kJ mol(-1) for the C-H BDE of 1,3-cyclopentadiene and 271 +/- 8 kJ mol(-1) for the enthalpy of formation of cyclopentadienyl radical. 相似文献
12.
OK Yoon WG Hwang JC Choe MS Kim 《Rapid communications in mass spectrometry : RCM》1999,13(14):1515-1521
A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
13.
The adsorption of OOH, the main product of the first step in the O2 reduction on Pt(1 1 1) surfaces, is studied on Pt-based bimetallic three-atom clusters. Cr, Co, and Ni are better adsorption sites for OOH than Pt, but the strong adsorption might not favor the dissociation of OOH. However, the presence of Cr, Co, or Ni in the vicinity of a Pt atom increases its electron density, enhancing the Pt ability to transfer electrons to oxygenated species. Thus, Cr, Co, or Ni in the subsurface, rather than on the exposed surface, may contribute favorably to catalyze the O2 reduction. 相似文献
14.
Agapito LA Maffei MG Salazar PF Seminario JM 《The journal of physical chemistry. A》2006,110(12):4260-4265
We introduce a posteriori multiplicity-based corrections to ab initio energies in order to reproduce experimental atomization energies. This simple approach, as compared to the alternative ones to improve density functionals and standard correlated methods, requires less computational resources than higher levels of theory. We extend our approach to include molecules containing second-row elements. Molecules are taken from the Gaussian sets for which experimental values are known with errors of less than 1 kcal/mol. We postulate that inexpensive multiplicity-based corrections can account for effects that are not accounted because of the low level of theory of the method or because of the small basis used for the calculations. 相似文献
15.
Perfluorobutyric Acid and Its Monohydrate: A Chirped Pulse and Cavity Based Fourier Transform Microwave Spectroscopic Study 下载免费PDF全文
Javix Thomas Agapito Serrato III Prof. Dr. Wei Lin Prof. Dr. Wolfgang Jäger Prof. Dr. Yunjie Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6148-6153
Rotational spectra of perfluorobutyric acid (PFBA) and its monohydrate were studied with a broadband chirped pulse and a narrow‐band cavity based Fourier transform microwave spectrometer, and high‐level ab initio calculations. Extensive conformational searches were performed for both the acid and its monohydrate at the MP2/6‐311++G(2d,p) level of theory. Two and three conformers were predicted to exist for PFBA and its monohydrate, respectively. One set of rotational transitions was observed and assigned for each, PFBA and its monohydrate. Based on the measured broadband spectra, we confidently conclude that only one dominant conformer exists in each case. The orientation of the hydroxyl group in PFBA was determined by using isotopic analysis. Comparison of the observed transition intensities and the calculated electric dipole moment components allowed us to identify the most stable monohydrate conformation, which takes on an insertion hydrogen‐bonding topology. Comparisons to the shorter chain analogues, that is, trifluoroacetic acid, perfluoropropionic acid, and their monohydrates, are made to elucidate the general trend in their conformational preference and binding topologies. 相似文献
16.
First, the basic concept of the vector derivative in geometric algebra is introduced. Second, beginning with the Fourier transform
on a scalar function we generalize to a real Fourier transform on Clifford multivector-valued functions
Third, we show a set of important properties of the Clifford Fourier transform on Cl3,0 such as differentiation properties, and the Plancherel theorem. Finally, we apply the Clifford Fourier transform properties
for proving an uncertainty principle for Cl3,0 multivector functions. 相似文献
17.
Agapito Jose Petrullo Pasquale Senato Domenico Torres Maria M. 《Journal of Algebraic Combinatorics》2021,54(2):457-473
Journal of Algebraic Combinatorics - Through the action of the Weyl algebra on the geometric series, we establish a generalization of the Worpitzky identity and new recursive formulae for a family... 相似文献
18.
19.
Relaxation of toroidal discharges is described by the principle of minimum energy dissipation together with the constraint
of conserved global helicity. The resulting Euler-Lagrange equation is solved in toroidal coordinates for an axisymmetric
torus by expressing the solutions in terms of Chandrasekhar-Kendall (C-K) eigenfunctions analytically continued in the complex
domain. The C-K eigenfunctions are obtained as hypergeometric functions that are solutions of scalar Helmholtz equation in
toroidal coordinates in the large aspect-ratio approximation. Equilibria are constructed by assuming the current to vanish
at the edge of plasma. For the m=0, n=0 (m and n are the poloidal and toroidal mode numbers respectively) relaxed states, the magnetic field, current, q (safety factor) and pressure profiles are calculated for a given value of aspect-ratio of the torus and for different values
of the eigenvalue λ
r
0. The new feature of the present model is that solutions allow for both tokamak as well as RFP-like behaviour with increase
in the values of λ
r
0, which is related directly to volt-sec in the experiment. 相似文献
20.
Seminario JM Maffei MG Agapito LA Salazar PF 《The journal of physical chemistry. A》2006,110(3):1060-1064
Energy correctors are introduced for the calculation of molecular energies of compounds containing first row atoms (Li-F) to modify ab initio molecular orbital calculations of energies to better reproduce experimental results. Four additive correctors are introduced to compensate for the differences in the treatment of molecules with different spin multiplicities and multiplicative correctors are also calculated for the electronic and zero-point vibrational energies. These correctors, individually and collectively yield striking improvements in the atomization energies for several ab initio methods. We use as training set the first row subset of molecules from the G1 basis of molecules; when the correctors are applied to other molecules not included in the training set, selected from the G3 basis, similar improvements in the atomization energies are obtained. The special case of the B3PW91/cc-pVTZ yields an average error of 1.2 kcal/mol, which is already within a chemical accuracy and comparable to the Gaussian-n theories accuracy. The very inexpensive B3PW91/6-31G** yields an average error of 2.1 kcal/mol using the correctors. Methods considered unsuitable for energetics such as HF and LSDA yield corrected energies comparable to those obtained with the best highly correlated methods. 相似文献