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1.
The second-order correlation energy of M?ller–Plesset perturbation theory is computed for the neon atom using a wave function
that depends explicitly on the interelectronic coordinates (MP2-R12). The resolution-of-identity (RI) approximation, which
is invoked in the standard formulation of MP2-R12 theory, is largely avoided by rigorously computing the necessary three-electron
integrals. The basis-set limit for the second-order correlation energy is reached to within 0.1 mE
h. A comparison with the conventional RI-based MP2-R12 method shows that only three-electron integrals over s and p orbitals need to be computed exactly, indicating that the RI approximation can be safely used for integrals involving orbitals
of higher angular momentum.
Received: 9 May 2001 / Accepted: 31 October 2001 / Published online: 9 January 2002 相似文献
2.
Rita Prosmiti Alexei A. Buchachenko Pablo Villarreal Gerardo Delgado-Barrio 《Theoretical chemistry accounts》2001,106(6):426-433
Ab initio molecular electronic structure calculations are performed for H5
+ at the QCISD(T) level of theory, using a correlation-consistent quadruple-zeta basis set. Structures, vibrational frequencies
and thermochemical properties are evaluated for ten stationary points of the H5
+ hypersurface and are compared with previous calculations. The features of the H3
+…H2 interaction at intermediate and large intermolecular distances are also investigated. Furthermore, an analytical functional
form for the potential-energy surface of H5
+ is derived using a first-order diatomics-in-molecule perturbation theory approach. Its topology is found to be qualitatively
correct for the short-range interaction region.
Received: 15 March 2001 / Accepted: 5 July 2001 / Published online: 11 October 2001 相似文献
3.
Using a systematic series of basis sets in supermolecular and symmetry-adapted intermolecular perturbation theory calculations
it is examined how interaction energies of various water dimer structures change upon addition and shifting of bond functions.
Their addition to augmented double- and triple-zeta basis sets brings the sum of the electron correlation contributions to
the second-order interaction energy nearly to convergence, while accurate first-order electrostatic and exchange contributions
require better than augmented quadruple-zeta quality. A scheme which combines the different perturbation energy contributions
as computed in different basis subsets performs uniformly well for the various dimer structures. It yields a symmetry-adapted
perturbation theory value of −21.08 kJ/mol for the energy of interaction of two vibrationally averaged water molecules compared
to −21.29 kJ/mol when the full augmented triple-zeta basis set is used throughout.
Received: 4 November 1999 / Accepted: 8 February 2000 / Published online: 12 May 2000 相似文献
4.
Low-spin/high-spin energy splittings for Fe(II) transition-metal complexes – particularly in weak ligand fields – cannot
be well described by density functional methods. Different density functionals yield results which differ by up to 1 eV in
transition-metal complexes with sulfur-rich first coordination spheres. We attribute this failure to the fact that the high-spin
state is systematically favoured in Hartree–Fock-type theories, because Fermi correlation is included in the exact exchange,
while Coulomb correlation is not. We thus expect that the admixture of exact exchange to a given density functional will heavily
influence the energy splitting between states of different multiplicity. We demonstrate that the energy splitting depends
linearly on the coefficient of exact exchange admixture. This remarkable result is found for all the Fe(II)–S complexes studied.
From this observation we conclude in connection with experimental results that Becke's 20% admixture should be reduced to
about 15% if meaningful energetics are sought for transition-metal compounds. We rationalize that this reduction by 5% will
not affect the quality of the hybrid functional since we arrive at a slightly modified functional, which lies between the
pure density functional and the hybrid density functional, which both give good results for “standard” systems.
Received: 13 July 2001 / Accepted: 31 August 2001 / Published online: 16 November 2001 相似文献
5.
The recent “chemical energy component analysis” permits the total energy of a molecule to be presented approximately but
to good accuracy as a sum of atomic and diatomic energy contributions. Here the diatomic energy components are further decomposed
into terms of different physical origin: electrostatics (in point-charge approximation and the distributed charge corrections),
exchange effects, diatomic overlap and atomic basis extension terms. This analysis may provide us with a deeper insight into
the factors influencing both the chemical bonds and the nonbonded interatomic interactions.
Received: 6 May 2002 / Accepted: 13 November 2002 / Published online: 19 March 2003
Acknowledgements. The authors are indebted to the Hungarian Scientific Research Fund for partial financial support (grant no. OTKA T29716).
Correspondence to: I. Mayer e-mail: mayer@chemres.hu 相似文献
6.
It is shown that the molecular energy calculated at the self-consistent-field level can be strictly expressed as a sum of
one- and two-atom energy components in the framework of Bader's topological theory of atoms in molecules (AIM). The expressions
of our recent “chemical energy component analysis” can be obtained from the AIM ones as some linear combination of atomic
orbitals mappings of the integrations over the atomic basins.
Received: 15 June 2000 / Accepted: 4 October 2000 / Published online: 19 January 2001 相似文献
7.
Methods are described to incorporate solvent reaction field effects into solute electronic structure calculations. Included
are several old and new approaches based on approximate solutions of Poisson's equation through boundary element methods,
wherein the solutions are represented in terms of certain apparent surface charge or apparent surface dipole distributions.
Practical algorithms to set up and solve the requisite equations are described and implemented in a new general reaction field
computer program. Illustrative computational results are presented to show the performance of the program.
Received: 2 July 2001 / Accepted: 11 September 2001 / Published online: 19 December 2001 相似文献
8.
Daniel M. Chipman 《Theoretical chemistry accounts》2002,107(2):80-89
Alternative ways are examined for representing a reaction field to treat the important effects of long-range electrostatic
interaction with a solvent in electronic structure calculations on the properties of a solute. Several extant boundary element
methods for approximate representation of the solvent reaction field in terms of surface charge distributions are considered,
and analogous new methods for approximate representation in terms of surface dipole distributions are introduced. Illustrative
computational results are presented on representative small neutral and ionic solutes to evaluate the relative accuracy of
various methods.
Received: 2 July 2001 / Accepted: 10 September 2001 / Published online: 19 December 2001 相似文献
9.
The ground state and several low-lying excited states of the Mg2 dimer have been studied by means of a combination of the complete-active-space multiconfiguration self-consistent-field (CASSCF)/CAS
multireference second-order perturbation theory (CASPT2) method and coupled-cluster with single and double excitations and
perturbative contribution of connected triple excitations [CCSD(T)] scheme. Reasonably good agreement with experiment has
been obtained for the CCSD(T) ground-state potential curve but the dissociation energy of the only experimentally known A1Σ
u
+ excited state of Mg2 is somewhat overestimated at the CASSCF/CASPT2 level. The spectroscopic constants D
e, R
e and ωe deduced from the calculated potential curves for other states are also reported. In addition, some spin–orbit matrix elements
between the excited singlet and triplet states of Mg2 have been evaluated as a function of internuclear separation.
Received: 10 May 2001 / Accepted: 15 August 2001 / Published online: 30 October 2001 相似文献
10.
H. Strømsnes S. Jusuf A. Bagatur'yants O. Gropen U. Wahlgren 《Theoretical chemistry accounts》2001,106(5):329-338
The convergence of chemisorption energy for hydrogen and oxygen on gold clusters is studied. Two theoretical approaches have
been employed; wavefunction methods at the self-consistent-field second–order M?ller–Plesset level and density functional
theory and the two methods are compared. Relativistic effective core potentials exploited in the former approach were developed
in this work.
Received: 25 October 1999 / Accepted: 21 February 2001 / Published online: 11 October 2001 相似文献
11.
Molecular mechanics minimizations based on the CVFF force field and molecular dynamics simulation for a time of 2.5 ns were
performed to examine the conformational behaviour and the molecular motion of acetylcholine in vacuo and in aqueous solution.
Five low-lying conformations, namely the TT, TG, GG, G*G and GT, were obtained from molecular mechanics computations with
the GT structure as the absolute minimum. Molecular dynamics trajectories in vacuo and in water show that only four (GT, GG,
G*G and TG) and three (TG, TT and GT) conformations are present in the simulation time, respectively. Density functional B3LYP
and second-order M?ller–Plesset (MP2) methods were then used to study all the five lowest-lying conformers of acetylcholine
neurotransmitter in vacuo and in water by the polarizable continuum model approach. The B3LYP and MP2 computations show that
in the gas phase all minima lie in a narrow range of energy with the G*G conformer as the most stable one. The relative minima
GG, GT, TG and TT are located at 1.1 (3.3), 1.8 (4.2), 2.1 (4.5) and 4.3 (7.3) kcal/mol above the absolute one at the B3LYP
(MP2) level. The preferred conformation in water is the TG. Solvation reduces the relative energy differences between the
five minima in both computations.
Received: 4 April 2001 / Accepted: 5 July 2001 / Published online: 30 October 2001 相似文献
12.
Amy J. Austin Michael J. Frisch John A. Montgomery George A. Petersson 《Theoretical chemistry accounts》2002,107(3):180-186
An overlap criterion is defined that connects the identification of core orbitals in a molecular system, which can be problematic,
to that in isolated atoms, which is well defined. This approach has been tested on a variety of troublesome systems that have
been identified in the literature, including molecules containing third-row main-group elements, and is shown to remove errors
of up to 100 kcal/mol arising from an inconsistent treatment of core orbitals at different locations on a potential-energy
surface. For some systems and choices of core orbitals, errors as large as 19 kcal/mol can be introduced even when consistent
sets of orbitals are frozen, and the new method is shown to identify these cases of substantial core–valence mixing. Finally,
even when there is limited core–valence mixing, the frozen-core approximation can introduce errors of more than 5 kcal/mol,
which is much larger than the presumed accuracy of models such as G2 and CBS-QB3. The source of these errors includes interatomic
core–core and core–valence dispersion forces.
Received: 31 August 2001 / Accepted: 11 October 2001 / Published online: 9 January 2002 相似文献
13.
Kinetic isotope effects, KIEs, for hydrogen abstraction from C2H6 and C2D6 by chlorine atom have been studied by the dual-level direct dynamics approach. A low-level potential energy surface is obtained
with the MNDO-SRP method. High-level structural properties of the reactants, transition state, and products were obtained
at the MP2 level with the cc-pVDZ, aug-cc-pVDZ, and the cc-pVTZ basis sets. Using the variational transition state theory
with microcanonical optimized multidimensional tunneling, the values of deuterium KIE, at 300 K, range from 2.28 to 3.27,
in good agreement with the experimental values (2.69–5.88).
Received: 6 June 2001 / Accepted: 12 July 2001 / Published online: 19 November 2001 相似文献
14.
Ramon Crehuet Josep Maria Bofill Josep Maria Anglada 《Theoretical chemistry accounts》2002,107(3):130-139
The mathematical structure of the reduced-gradient-following (RGF) path introduced by Quapp et al. (1988 J. Comput. Chem. 19:1087) is reviewed and analyzed. We report two new algorithms to evaluate the RGF path. The RGF path is also compared mathematically
and computationally with the gradient extremals path. An example of the evaluation of the RGF path is also reported.
Received: 21 May 2001 / Accepted: 27 September 2001 / Published online: 9 January 2002 相似文献
15.
Sándor Kristyán Adrienn Ruzsinszky Gábor I. Csonka 《Theoretical chemistry accounts》2001,106(6):404-411
Experimental enthalpies of formation have been approximated using single-point Hartree–Fock (HF)–self-consistent-field (SCF)
total energies plus the rapid estimation of basis set error and correlation energy from partial charges (REBECEP) energy corrections.
The energy corrections are calculated from the HF–SCF partial atomic charges and optimized atomic energy parameters. The performance
of the method was tested on 51 closed-shell neutral molecules (50 molecules from the G3/99 thermochemistry database plus urea,
composed of H, C, N, O, and F atoms). The predictive force of the method is demonstrated, because these larger molecules were
not used for the optimization of the atomic parameters. We used the earlier RECEP-3 [HF/6-311+G(2d,p)] and REBECEP [HF/6-31G(d)]
atomic parameter sets obtained from the G2/97 thermochemistry database (containing small molecules) together with natural
population analysis and Mulliken partial charges. The best results were obtained using the natural population analysis charges,
although the Mulliken charges also provide useful results. The root-mean-square deviations from the experimental enthalpies
of formation for the selected 51 molecules are 1.15, 3.96, and 2.92 kcal/mol for Gaussian-3, B3LYP/6-11+G(3df,2p), and REBECEP
(natural population analysis) enthalpies of formation, respectively (the corresponding average absolute deviations are 0.94,
7.09, and 2.27 kcal/mol, respectively). The REBECEP method performs considerably better for the 51 test molecules with a moderate
6-31G(d) basis set than the B3LYP method with a large 6-311+G(3df,2p) basis set.
Received: 10 March 2001 / Accepted: 5 July 2001 / Published online: 11 October 2001 相似文献
16.
The equilibrium geometries, electronic structures and UV–vis spectra of a series of spiroannelated quinone-type methanofullerenes
have been determined by using Zerner's intermediate neglect of differential overlap method. The results show that between
fullerene and the addend there exists a special interaction, “periconjugation”, which results in through-space orbital interactions.
The calculated UV–vis spectra are in good agreement with experiments. On the basis of the electronic spectra, the β values
are calculated. The results show that spiroannelated quinone-type methanofullerenes have quite large β values. We attribute
the large β values to both the charge transfer from C60 to benzoquinone and on the C60 three-dimensional conjugated sphere.
Received: 17 December 2000 / Accepted: 16 March 2001 / Published online: 13 June 2001 相似文献
17.
The hydrogen-ion molecule has been used as a test system for the application of the Schr?dinger–Riccati formulation to molecular
calculations. Some of the points discussed are the characteristics (quasiconstancy of the local energies, size, number of
points) of the sampling region to be chosen, the dependence on the starting function, the precision of the calculations, and
the excellent behaviour of the predicted function (by comparison to an accurate function).
Received: 1 May 2001 / Accepted: 25 July 2001 / Published online: 11 October 2001 相似文献
18.
J. F. Ogilvie S.-L. Cheah Y.-P. Lee S. P. A. Sauer 《Theoretical chemistry accounts》2002,108(2):85-97
From quantum-chemical calculations of rotational g factor and new experimental measurements of strengths of lines in infrared spectra of vibration–rotational bands v′–0 in absorption, with 1≤v′≤4, of 12C16O, and from analysis of 16,947 frequencies and wave numbers assigned to pure rotational and vibration–rotational transitions
within electronic ground state X
1Σ+, including new measurements of band 4–0 of 12C16O, we evaluate radial functions for potential energy and electric dipolar moment, the latter both in polynomial form and as
a rational function that has qualitatively correct behaviour under limiting conditions.
Received: 8 November 2001 / Accepted: 5 February 2002 / Published online: 14 August 2002 相似文献
19.
Monte Carlo simulations have been carried out for 2-ethoxyethanol (C2E1) in isothermal-isobaric ensemble (NPT) at different temperatures and 1 atm pressure with a continuum configurational biased
procedure in water and chloroform media. Hydrogen bond bridges were formed between adjacent oxygen atoms in C2E1 (CH3CH2OCH2CH2OH) through water molecules. We also found that the stable conformers of C2E1 in water and CHCl3 are different and the effect of temperature on solute-solvent interaction energies is considerable. The self-association
of C2E1 in aqueous and nonaqueous media has been studied by statistical perturbation theory, and the relative free energy has been
obtained at different reaction coordinates by double-wide sampling method. Two minima were found in water solvent in the potential
of mean force (PMF), corresponding to the contact and solvent-separated pairs, but only one minimum was found in CHCl3 solvent corresponding to a contact pair complex.
Received: 18 January 2001 / Accepted: 22 October 2001 / Published online: 21 January 2002 相似文献
20.
Georg Jansen 《Theoretical chemistry accounts》2000,104(6):499-506
It is shown that the multipole expansion of each order of the polarization series converges for large enough intermolecular
distances when finite basis sets of Gaussian or Slater-type functions are used to approximate molecular response properties.
Convergence of the multipole expansion for each order of the polarization series does not imply convergence of the polarization
series itself. A corresponding convergence condition is extracted from the general perturbation theory in a finite-dimensional
space and is applied to the H + H+ problem.
Received: 29 September 1999 / Accepted: 22 May 2000 / Published online: 18 August 2000 相似文献