Frontier orbital consistent quantum capping potential (FOC-QCP) for bulky ligand of transition metal complexes

Chemically reasonable models of PR3 (R = Me, Et, iPr, and tBu) were constructed to apply the post Hartree-Fock method to large transition metal complexes. In this model, R is replaced by the H atom including the frontier orbital consistent quantum capping potential (FOC-QCP) which reproduces the frontier orbital energy of PR3. The steric effect is incorporated by the new procedure named steric repulsion correction (SRC). To examine the performance of this FOC-QCP method with the SRC, the activation barriers and reaction energies of the reductive elimination reactions of C2H6 and H2 from M(R1)2(PR2(3))2 (M = Ni, Pd, or Pt; R1 = Me for R2 = Me, Et, or iPr, or R1 = H for R2 = tBu) were evaluated with the DFT[B3PW91], MP4(SDQ), and CCSD(T) methods. The FOC-QCP method reproduced well the DFT[B3PW91]- and MP4(SDQ)-calculated energy changes of the real complexes with PMe3. For more bulky phosphine, the SRC is important to present correct energy change, in which the MP2 method presents reliable steric repulsion correction like the CCSD(T) method because the systems calculated in the SRC do not include a transition metal element. The monomerization energy of [RhCl(PiPr3)2]2 and the coordination energies of CO, H2, N2, and C2H4 with [RhCl(PiPr3)2]2 were theoretically calculated by the CCSD(T) method combined with the FOC-QCP and the SRC. The CCSD(T)-calculated energies agree well with the experimental ones, indicating the excellent performance of the combination of the FOC-QCP with the SRC. On the other hand, the DFT[B3PW91]-calculated energies of the real complexes considerably deviate from the experimental ones.     

Theoretical study of Pt(PR3)(2)(AlCl3) (R = H, Me, Ph, or Cy) including an unsupported bond between transition metal and non-transition metal elements: geometry, bond strength, and prediction

The molecular structure and the binding energy of Pt(PR(3))(2)(AlCl(3)) (R = H, Me, Ph, or Cy) were investigated by DFT, MP2 to MP4(SDTQ), and CCSD(T) methods. The optimized structure of Pt(PCy(3))(2)(AlCl(3)) (Cy = cyclohexyl) by the DFT method with M06-2X and LC-BLYP functionals agrees well with the experimental one. The MP4(SDTQ) and CCSD(T) methods present similar binding energies (BE) of Pt(PH(3))(2)(AlCl(3)), indicating that these methods provide reliable BE value. The DFT(M06-2X)-calculated BE value is close to the MP4(SDTQ) and CCSD(T)-calculated values, while the other functionals present BE values considerably different from the MP4(SDTQ) and CCSD(T)-calculated values. All computational methods employed here indicate that the BE values of Pt(PMe(3))(2)(AlCl(3)) and Pt(PPh(3))(2)(AlCl(3)) are considerably larger than those of the ethylene analogues. The coordinate bond of AlCl(3) with Pt(PR(3))(2) is characterized to be the σ charge transfer (CT) from Pt to AlCl(3). This complex has a T-shaped structure unlike the well-known Y-shaped structure of Pt(PMe(3))(2)(C(2)H(4)), although both are three-coordinate Pt(0) complex. This T-shaped structure results from important participation of the Pt d(σ) orbital in the σ-CT; because the Pt d(σ) orbital energy becomes lower as the P-Pt-P angle decreases, the T-shaped structure is more favorable for the σ-CT than is the Y-shaped structure. [Co(alcn)(2)(AlCl(3))](-) (alcn = acetylacetoneiminate) is theoretically predicted here as a good candidate for the metal complex, which has an unsupported M-Al bond because its binding energy is calculated to be much larger than that of Pt(PCy(3))(2)(AlCl(3)).     

Density functional theory and post-Hartree-Fock studies on molecular structure and harmonic vibrational spectrum of formaldehyde

Density functional theory (DFT) with the Becke's three-parameter exchange correlation functional and the functional of Lee, Yang and Parr, gradient-corrected functionals of Perdew, and Perdew and Wang [the DFT(B3LYP), DFT(B3P86) and DFT(B3PW91) methods, respectively], and several levels of conventional ab initio post-Hartree-Fock theory (second- and fourth-order perturbation theory M?ller-Plesset MP2 and MP4(SDTQ), coupled cluster with the single and double excitations (CCSD), and CCSD with perturbative triple excitation [CCSD(T)], configuration interaction with the single and double excitations [CISD], and quadratic configuration interaction method [QCISD(T)], using several basis sets [ranging from a simple 6-31G(d,p) basis set to a 6-311+ +G(3df, 2pd) one], were applied to study of the molecular structure (geometrical parameters, rotational constants, dipole moment) and harmonized infrared (IR) spectrum of formaldehyde (CH₂O). High-level ab initio methods CCSD(T) and QCISD(T) with the 6-311+ +G(3df, 2pd) predict correctly molecular parameters, vibrational harmonic wavenumbers and the shifts of the harmonic IR spectrum of ¹²CH₂ ¹⁶O upon isotopic substitution. Received: 30 January 1997 / Accepted: 7 May 1997     

Ab initio calculation of bowl, cage, and ring isomers of C20 and C20-

High-level ab initio calculations have been carried out to reexamine relative stability of bowl, cage, and ring isomers of C(20) and C(20)(-). The total electronic energies of the three isomers show different energy orderings, strongly depending on the hybrid functionals selected. It is found that among three popular hybrid density-functional (DF) methods B3LYP, B3PW91, PBE1PBE, and a new hybrid-meta-DF method TPSSKCIS, only the PBE1PBE method (with cc-pVTZ basis set) gives qualitatively correct energy ordering as that predicted from ab initio CCSD(T)/cc-pVDZ [CCSD(T)-coupled-cluster method including singles, doubles, and noniterative perturbative triples; cc-pVDZ-correlation consistent polarized valence double zeta] as well as from MP4(SDQ)/cc-pVTZ [MP4-fourth-order Moller-Plesset; cc-pVTZ-correlation consistent polarized valence triple zeta] calculations. Both CCSD(T) and MP4 calculations indicate that the bowl is most likely the global minimum of neutral C(20) isomers, followed by the fullerene cage and ring. For the anionic counterparts, the PBE1PBE calculation also agrees with MP4/cc-pVTZ calculation, both predicting that the bowl is still the lowest-energy structure of C(20)(-) at T=0 K, followed by the ring and the cage. In contrast, both B3LYP/cc-pVTZ and B3PW91/cc-pVTZ calculations predict that the ring is the lowest-energy structure of C(20)(-). Apparently, this good reliability in predicting the energy ordering renders the hybrid PBE method a leading choice for predicting relative stability among large-sized carbon clusters and other carbon nanostructures (e.g., finite-size carbon nanotubes, nano-onions, or nanohorns). The relative stabilities derived from total energy with Gibbs free-energy corrections demonstrate a changing ordering in which ring becomes more favorable for both C(20) and C(20)(-) at high temperatures. Finally, photoelectron spectra (PES) for the anionic C(20)(-) isomers have been computed. With binding energies up to 7 eV, the simulated PES show ample spectral features to distinguish the three competitive C(20)(-) isomers.     

Theoretical investigation of the binding energies of the iodide ion and xenon atom with decaborane

The interaction of decaborane (B(10)H(14)) with the I(-) ion and the (isoelectronic) Xe atom is investigated using a number of theoretical methods: MP2, CCSD(T), CCSD, spin-orbit CISD, and DFT using the B3LYP, B3PW91, PW91PW91, and PBE0 methods. All non-DFT and some DFT methods agree that B(10)H(14)I(-) is bound by charge-dipole electrostatic forces, charge- and dipole-induced-dipole forces, and dispersion forces, while B(10)H(14)Xe is bound by dipole-induced-dipole forces and dispersion forces. Counterpoise corrections are necessary to obtain reliable results. Relativistic effective core potentials were used for the I, Xe, and B atoms. Basis sets for use with these potentials are discussed as is the question of basis set balance in molecules. We find B(10)H(14)I(-) to be bound by 19.8 kcal/mol and B(10)H(14)Xe by 1.1 kcal/mol, indicating that the charge and polarizability of I(-) play the major role in the interaction energy.     

Computational studies on ethylene addition to nickel bis(dithiolene)

The density functionals B3LYP, B3PW91, BMK, HSE06, LC-ωPBE, M05, M06, O3LYP, TPSS, ω-B97X, and ω-B97XD are used to optimize key transition states and intermediates for ethylene addition to Ni(edt)(2) (edt = S(2)C(2)H(2)). The efficacy of the basis sets 6-31G**, 6-31++G**, cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ is also examined. The geometric parameters optimized with different basis sets and density functionals are similar and agree well with experimental values. The ω-B97XD functional gives relative energies closest to those from CCSD, while M06 and HSE06 yield results close to those from CCSD(T). CASSCF and CASSCF-PT2 calculation results are also given. Variation of the relative energies from different density functionals appears to arise, in part, from the multireference character of this system, as confirmed by the T1 diagnostic and CASSCF calculations.     

Theoretical study on the potential energy surface of NC<Subscript>3</Subscript>P isomers

Density functional theory (DFT) calculations have been used to study the isomerization process in the NC₃P system. At the DFT/B3LYP/6-311G(d) level, 28 triplet and 28 singlet minima were obtained on their respective potential energy surfaces. The linear triplet ³NCCCP is the lowest-energy structure among the isomers. On the triplet PES, only linear isomers ³NCCCP, ³CNCCP, ³CCCNP, and ³CCNCP possess great kinetic and thermodynamic stabilities to exist under low-temperature conditions (such as in the dense interstellar clouds). At the same time, one chain-like and four three-membered-ring isomers on the singlet PES have been located with high kinetic and thermodynamic stabilities. Further CCSD(T)/6-311G(2df)//QCISD/6-311G(d), CCSD(T)/cc-pVTZ//DFT/B3LYP/cc-pVTZ, and CASPT2(14,12)/cc-pVQZ//CASSCF(14,12)/cc-p VQZ calculations are performed on the structures, frequencies, and energies of the relevant species. The bonding natures were analyzed and the results were compared with the analogous NC₃N and NC₂P molecules so as to aid their future experimental or astrophysical detection.     

Accurate interaction energies of hydrogen-bonded nucleic acid base pairs

Hydrogen-bonded nucleic acids base pairs substantially contribute to the structure and stability of nucleic acids. The study presents reference ab initio structures and interaction energies of selected base pairs with binding energies ranging from -5 to -47 kcal/mol. The molecular structures are obtained using the RI-MP2 (resolution of identity MP2) method with extended cc-pVTZ basis set of atomic orbitals. The RI-MP2 method provides results essentially identical with the standard MP2 method. The interaction energies are calculated using the Complete Basis Set (CBS) extrapolation at the RI-MP2 level. For some base pairs, Coupled-Cluster corrections with inclusion of noniterative triple contributions (CCSD(T)) are given. The calculations are compared with selected medium quality methods. The PW91 DFT functional with the 6-31G basis set matches well the RI-MP2/CBS absolute interaction energies and reproduces the relative values of base pairing energies with a maximum relative error of 2.6 kcal/mol when applied with Becke3LYP-optimized geometries. The Becke3LYP DFT functional underestimates the interaction energies by few kcal/mol with relative error of 2.2 kcal/mol. Very good performance of nonpolarizable Cornell et al. force field is confirmed and this indirectly supports the view that H-bonded base pairs are primarily stabilized by electrostatic interactions.     

Conformations and energetics of sulfur and selenium diimides

The geometries and energetics of different conformations of sulfur and selenium diimides E(NR)(2) (E = S, Se; R = H, Me, (t)Bu, C(6)H(3)Me(2)-2,6, SiMe(3)) have been studied by using various ab initio and DFT molecular orbital techniques. The syn,syn conformation is found to be most stable for parent E(NH)(2), but in general, the preferred molecular conformation for substituted chalcogen diimides is syn,anti. In the case of E(NH)(2) the present calculations further confirm that syn,syn and syn,anti conformations lie energetically close to each other. From the three different theoretical methods used, B3PW91/6-31G proved to be the most suitable method for predicting the geometries of chalcogen diimides. The optimized geometrical parameters are in a good agreement with all available experimental data. While qualitative energy ordering of the different conformations is independent of the level of theory, the quantitative energy differences are dependent on the method used. The performance and reliability of higher level ab initio calculations and DFT methods using large basis sets were tested and compared with experimental information where available. All of the higher level ab inito methods give very similar results, but the use of large basis sets with the B3PW91 method does not increase the reliability of the results. The combination of CCSD(T)/cc-pVDZ with the B3PW91/6-31G-optimized geometries is found to be the method of choice to study energetic properties of chalcogen diimides.     

Can large active-space CASSCF calculation make sense to the reaction analysis of iron complex? A benchmark study of methane oxidation reaction by FeO+

A methane oxidation reaction by FeO⁺ cation was theoretically investigated based on the density functional theory (DFT) and the complete active-space self-consistent field (CASSCF) method as well as the coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) to explore the active-space dependency to computational analyses in such strongly correlated reaction systems. A small active-space CASSCF(5e in 5o) calculation, which only includes five 3d orbitals of the Fe atom in the active-space, showed remarkable difference both in energy and geometry compared to those computed by the DFT and CCSD(T) methods. Interestingly, a large active-space CASSCF(17e in 17o) calculation, which includes almost all the valence orbitals gives a qualitative agreement with either the DFT or the CCSD(T) results in the first half part of the reaction, although it varies from them in the latter half part. Therefore, it is indicated that the active-space dependency is serious in some part of the reaction and the small active-space CASSCF might lead a wrong discussion. We further investigated the optimized geometry of the intermediate complex with the small and the large active-space CASSCF methods as well as the CCSD(T) method, and found that the CASSCF(5e in 5o)-optimized geometry is considerably different from the others. In consequence, a small active-space CASSCF/CASPT2 calculation does not really work for such a strongly correlated reaction system even qualitatively, and a sophisticated assessment using the large active-space CASSCF/CASPT2 method will be indispensable. © 2018 Wiley Periodicals, Inc.     

三氟化氯和环氧丙烷反应的理论研究

应用密度泛函理论对三氟化氯和环氧丙烷反应产生C3H5O和C1F2自由基的机理进行了研究。在B3PW91/6-31+G(d,p)水平优化了12个不同反应通道上各驻点(反应物、中间体、过渡态和产物) 的几何构型,并计算了它们的振动频率和零点振动能。采用CCSD(T)/6-31+ G(d,p) // B3PW91/6-31+G(d,p)单点能计算方法求得各物种的能量,并作了零点能校正。计算结果表明,三氟化氯和环氧丙烷反应可经过不同的反应路径引发C3H5O自由基和C1F2自由基,其中,三氟化氯呈对称的F原子与环氧丙烷的C(1)上与CH3在同一侧的上的H原子结合的活化能最低,仅为16.81 kJ/mol。     

Pi and sigma-phenylethynyl radicals and their isomers o-, m-, and p-ethynylphenyl: structures, energetics, and electron affinities

Molecular structures, energetics, vibrational frequencies, and electron affinities are predicted for the phenylethynyl radical and its isomers. Electron affinities are computed using density functional theory, -namely, the BHLYP, BLYP, B3LYP, BP86, BPW91, and B3PW91 functionals-, employing the double-zeta plus polarization DZP++ basis set; this level of theory is known to perform well for the computation of electron affinities. Furthermore, ab initio computations employing perturbation theory, coupled cluster with single and double excitations [CCSD], and the inclusion of perturbative triples [CCSD(T)] are performed to determine the relative energies of the isomers. These higher level computations are performed with the correlation consistent family of basis sets cc-pVXZ (X = D, T, Q, 5). Three electronic states are probed for the phenylethynyl radical. In C2v symmetry, the out-of-plane (2B1) radical is predicted to lie about 10 kcal/mol below the in-plane (2B2) radical by DFT methods, which becomes 9.4 kcal/mol with the consideration of the CCSD(T) method. The energy difference between the lowest pi and sigma electronic states of the phenylethynyl radical is also about 10 kcal/mol according to DFT; however, CCSD(T) with the cc-pVQZ basis set shows this energy separation to be just 1.8 kcal/mol. The theoretical electron affinities of the phenylethynyl radical are predicted to be 3.00 eV (B3LYP/DZP++) and 3.03 eV (CCSD(T)/DZP++//MP2/DZP++). The adiabatic electron affinities (EAad) of the three isomers of phenylethynyl, that is, the ortho-, meta-, and para-ethynylphenyl, are predicted to be 1.45, 1.40, and 1.43 eV, respectively. Hence, the phenylethynyl radical binds an electron far more effectively than the three other radicals studied. Thermochemical predictions, such as the bond dissociation energies of the aromatic and ethynyl C-H bonds and the proton affinities of the phenylethynyl and ethynylphenyl anions, are also reported.     

Density functional theory and the correlation consistent basis sets: the tight d effect on HSO and HOS

The HSO and HOS isomers have been revisited using the DFT functionals, B3LYP, B3PW91, and PBE, in combination with tight d-augmented correlation consistent basis sets, cc-pV(x+d)Z and aug-cc-pV(x+d)Z for second-row atoms. Structures, vibrationally averaged structures, relative energies, harmonic and anharmonic frequencies, enthalpies of formation of HSO and HOS, and the barrier for the HSO/HOS isomerization have been determined. These results were compared with results from previous DFT and ab initio studies in which the standard correlation consistent basis sets were used. The relative energies of the two isomers converge more rapidly and smoothly with respect to increasing basis set size for the tight d-augmented sets than for the standard basis sets. Our best calculations, B3PW91/aug-cc-pV(5+d)Z, for the relative energy of the isomers are in excellent agreement with previous CCSD(T) results given by Wilson and Dunning.     

Intermolecular potentials of the silane dimer calculated with Hartree-Fock theory, Møller-Plesset perturbation theory, and density functional theory

We have calculated the intermolecular interaction potentials of the silane dimer at the D3d conformation using the Hartree-Fock (HF) self-consistent theory, the correlation-corrected second-order M?ller-Plesset (MP2) perturbation theory, and the density functional theory (DFT) with 108 functionals chosen from the combinations of 9 exchange and 12 correlation functionals. Single-point coupled cluster [CCSD(T)] calculations have also been carried out to calibrate the correlation effect. The HF calculations yield unbound potentials largely because of the exchange-repulsion interaction. In the MP2 calculations, the basis set effects on the repulsion exponent, the equilibrium bond length, the binding energy, and the asymptotic behavior of the calculated intermolecular potentials have been thoroughly studied. We have employed basis sets from the Slater type orbitals fitted with Gaussian functions (STO-nG, n = 3 approximately 6), Pople's medium size basis sets [up to 6-311++G(3df,3pd)], to Dunning's correlation consistent basis sets (cc-pVXZ and aug-cc-pVXZ, X = D, T, Q). With increasing basis size, the repulsion exponent and the equilibrium bond length converge at the 6-31G** basis set and the 6-311++G(3d,3p) basis set, respectively, while a large basis set (aug-cc-pVTZ) is required to converge the binding energy at a chemical accuracy ( approximately 0.05 kcal/mol). Up to the largest basis set used, the asymptotic dispersion coefficient has not converged to the expected C6 value from molecular polarizability calculations. We attribute the slow convergence partly to the inefficacy of using the MP2 calculations with Gaussian type functions to model the asymptotic behavior. Both the basis set superposition error (BSSE) corrected and uncorrected results are presented to emphasize the importance of including such corrections. Only the BSSE corrected results systematically converge to the expected potential curve with increasing basis size. The DFT calculations generate a wide range of interaction patterns, from purely unbound to strongly bound, underestimating or overestimating the binding energy. The binding energies calculated using the OPTXHCTH147, PBEVP86, PBEP86, PW91TPSS, PW91PBE, and PW91PW91 functionals and the equilibrium bond lengths calculated using the MPWHCTH93, TPSSHCTH, PBEVP86, PBEP86, PW91TPSS, PW91PBE, and PW91PW91 functionals are close to the MP2 results using the 6-311++G(3df,3pd) basis set. A correlation between the calculated DFT potentials and the exchange and correlation enhancement factors at the low-density region has been elucidated. The asymptotic behaviors of the DFT potentials are also analyzed.     

The Ni + O2 reaction: a combined IR matrix isolation and theoretical study of the formation and structure of NiO2

The reaction of Ni atoms with molecular oxygen has been reinvestigated experimentally in neon matrices and theoretically at the DFT PW91PW91/6311G(3df) level. Experimental results show that i) the nature of the ground electronic state of the superoxide metastable product is the same in neon and argon matrices, ii) two different photochemical pathways exist for the conversion of the superoxide to the dioxide ground state (involving 1.6 or 4 eV photons) and iii) an important matrix effect exists in the Ni + O(2)--> Ni(O(2)) or ONiO branching ratios. Theoretical results confirm that the electronic ground state of the metastable superoxide corresponds to the singlet state, in agreement with former CCSD(T) calculations, but in contradiction with other recent works. Our results show that the ground electronic state of the dioxide is (1)Sigma(+)(g) with the lowest triplet and quintet states at slightly higher energy, consistent with the observation of weak vibronic transitions in the near infrared. The potential energy profiles are modelled for the ground state and nine electronic excited states and a pathway for the Ni(triplet) + O(2)(triplet) --> Ni(O(2)) or ONiO (singlet) reaction is proposed, as well as for the Ni(O(2)) --> ONiO photochemical reaction, accounting for the experimental observations.     

Comparison of aromatic NH···π, OH···π, and CH···π interactions of alanine using MP2, CCSD, and DFT methods

A comparison of the performance of various density functional methods including long‐range corrected and dispersion corrected methods [MPW1PW91, B3LYP, B3PW91, B97‐D, B1B95, MPWB1K, M06‐2X, SVWN5, ωB97XD, long‐range correction (LC)‐ωPBE, and CAM‐B3LYP using 6‐31+G(d,p) basis set] in the study of CH···π, OH···π, and NH···π interactions were done using weak complexes of neutral (A) and cationic (A⁺) forms of alanine with benzene by taking the Møller–Plesset (MP2)/6‐31+G(d,p) results as the reference. Further, the binding energies of the neutral alanine–benzene complexes were assessed at coupled cluster (CCSD)/6‐31G(d,p) method. Analysis of the molecular geometries and interaction energies at density functional theory (DFT), MP2, CCSD methods and CCSD(T) single point level reveal that MP2 is the best overall performer for noncovalent interactions giving accuracy close to CCSD method. MPWB1K fared better in interaction energy calculations than other DFT methods. In the case of M06‐2X, SVWN5, and the dispersion corrected B97‐D, the interaction energies are significantly overrated for neutral systems compared to other methods. However, for cationic systems, B97‐D yields structures and interaction energies similar to MP2 and MPWB1K methods. Among the long‐range corrected methods, LC‐ωPBE and CAM‐B3LYP methods show close agreement with MP2 values while ωB97XD energies are notably higher than MP2 values. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010     

A theoretical study of the thermodynamics and kinetics of small organosulfur compounds

The performance of a large set of ab initio procedures in predicting geometries, thermochemical and kinetic data of small sulfur compounds is assessed. Geometries and thermochemical data for H₂S, (CH₃)₂S, H₂S₂, (CH₃)₂S₂ and H₂C=S are studied using the HF method, density functional theory methods (B3LYP, BHandHLYP, MPW1PW91 and BMK), post-HF methods [MP2, MP3, MP4, CCSD, CCSD(T) and QCISD] and composite techniques (G3, G3B3, CBS-QB3 and W1U). A set of five reactions involving these small organosulfur compounds is studied and the influence of the level of theory on transition state geometries, reaction barriers and rate coefficients is assessed. Independent of the level of theory used, accurate geometries are obtained with the 6-311G(2d,d,p) and cc-pVTZ basis sets, both reproducing experimental bond lengths and bond angles within 2 pm and 0.5°. Besides composite methods, the BMK/cc-pVTZ method is the only studied method that succeeds to predict standard enthalpies of formation within 10 kJ mol^?1 of the experimental data. The best agreement with experimental rate coefficients is obtained with the BHandHLYP/cc-pVTZ method, closely followed by the composite methods and the BMK/cc-pVTZ method. All these methods succeed to reproduce the experimental rate coefficients within a factor 4. To obtain an accurate prediction of both thermochemical and kinetic data for organosulfur compounds, the commonly used composite methods G3B3 and CBS-QB3 and the BMK/cc-pVTZ method prove to be valuable tools.     

Which density functional is close to CCSD accuracy to describe geometry and interaction energy of small noncovalent dimers? A benchmark study using Gaussian09

A benchmark study on all possible density functional theory (DFT) methods in Gaussian09 is done to locate functionals that agree well with CCSD/aug‐cc‐pVTZ geometry and Ave‐CCSD(T)/(Q‐T) interaction energy (E_int) for small non‐covalently interacting molecular dimers in “dispersion‐dominated” (class 1), “dipole‐induced dipole” (class 2), and “dipole‐dipole” (class 3) classes. A DFT method is recommended acceptable if the geometry showed close agreement to CCSD result (RMSD < 0.045) and E_int was within 80–120% accuracy. Among 382 tested functionals, 1–46% gave good geometry, 13–44% gave good E_int, while 1–33% satisfied geometry and energy criteria. Further screening to locate the best performing functionals for all the three classes was made by counting the acceptable values of energy and geometry given by each functionals. The meta‐generalized gradient approximation (GGA) functional M06L was the best performer with total 14 hits; seven acceptable energies and seven acceptable geometries. This was the only functional “recommended” for at least two dimers in each class. The functionals M05, B2PLYPD, B971, mPW2PLYPD, PBEB95, and CAM‐B3LYP gave 11 hits while PBEhB95, PW91B95, Wb97x, BRxVP86, BRxP86, HSE2PBE, HSEh1PBE, PBE1PBE, PBEh1PBE, and PW91TPSS gave 10 hits. Among these, M05, B971, mPW2PLYPD, Wb97x, and PW91TPSS were among the “recommended” list of at least one dimer from each class. Long‐range correction (LC) of Hirao and coworkers to exchange‐correlation functionals showed massive improvement in geometry and E_int. The best performing LC‐functionals were LC‐G96KCIS and LC‐PKZBPKZB. Our results predict that M06L is the most trustworthy DFT method in Gaussian09 to study small non‐covalently interacting systems. © 2013 Wiley Periodicals, Inc.     

Conventional strain energies of 1,2-dihydroazete, 2,3-dihydroazete, 1,2-dihydrophosphete, and 2,3-dihydrophosphete

The conventional strain energies of 1,2-dihydroazete, 2,3-dihydroazete, 1,2-dihydrophosphete, and 2,3-dihydrophosphete are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies and zero-point vibrational energies are computed for all pertinent molecular systems using SCF theory, second-order perturbation theory, and density functional theory and employing the correlation consistent basis sets cc-pVDZ, cc-pVTZ, and cc-pVQZ. Single-point fourth-order perturbation theory, CCSD, and CCSD(T) calculations employing the cc-pVTZ and the cc-pVQZ basis sets are computed using the MP2/cc-pVTZ and MP2/cc-pVQZ optimized geometries, respectfully, to ascertain the contribution of higher order correlation. Three DFT functionals, B3LYP, wB97XD, and M06-2X, are employed to determine whether they can yield results similar to those obtained at the CCSD(T) level.