Search results for " function"
showing 10 items of 9395 documents
Place-based policy in southern Italy: evidence from a dose-response approach
2021
This paper evaluates the effectiveness at a territorial level of a place-based policy for southern Italy, that is, territorial integrated projects (TIPs). We combine classical counterfactual designs and the construction of a dose–response function to assess the impact of the infrastructural interventions on the municipalities involved in a target region (Sicily). The results are robust enough to show policy effectiveness on both the number of workers and the number of plants. In the latter case, we also identify a significant and increasing dose–response function highlighting the positive relationship between funding intensity and the growth of plants.
An orbital-invariant internally contracted multireference coupled cluster approach.
2011
We have formulated and implemented an internally contracted multireference coupled cluster (ic-MRCC) approach aimed at solving two of the problems encountered in methods based on the Jeziorski-Monkhorst ansatz: (i) the scaling of the computational and memory costs with respect to the number of references, and (ii) the lack of invariance of the energy with respect to rotations among active orbitals. The ic-MRCC approach is based on a straightforward generalization of the single-reference coupled cluster ansatz in which an exponential operator is applied to a multiconfigurational wave function. The ic-MRCC method truncated to single and double excitations (ic-MRCCSD) yields very accurate pote…
Analytic second derivatives for general coupled-cluster and configuration-interaction models.
2004
Analytic second derivatives of energy for general coupled-cluster (CC) and configuration-interaction (CI) methods have been implemented using string-based many-body algorithms. Wave functions truncated at an arbitrary excitation level are considered. The presented method is applied to the calculation of CC and CI harmonic frequencies and nuclear magnetic resonance chemical shifts up to the full CI level for some selected systems. The present benchmarks underline the importance of higher excitations in high-accuracy calculations.
Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz.
2008
Spin-orbit splittings for (2)Pi states are calculated within coupled-cluster (CC) theory via first-order degenerate perturbation theory. Using the equation-of-motion CC variant for ionization potentials (EOMIP-CC), the two components of the considered (2)Pi state are treated in a balanced way by generating both radical states via annihilation of one electron out of the CC wave function of the corresponding anion. We report on the implementation of the described approach within the CC singles and doubles approximation. To ensure computational efficiency, an atomic mean-field approximation for the spin-orbit integrals is used, resulting in a formulation in terms of one-electron transition-den…
Linear-response theory for Mukherjee's multireference coupled-cluster method: Excitation energies
2012
The recently presented linear-response function for Mukherjee's multireference coupled-cluster method (Mk-MRCC) [T.-C. Jagau and J. Gauss, J. Chem. Phys. 137, 044115 (2012)] is employed to determine vertical excitation energies within the singles and doubles approximation (Mk-MRCCSD-LR) for ozone as well as for o-benzyne, m-benzyne, and p-benzyne, which display increasing multireference character in their ground states. In order to assess the impact of a multireference ground-state wavefunction on excitation energies, we compare all our results to those obtained at the single-reference coupled-cluster level of theory within the singles and doubles as well as within the singles, doubles, and…
Molecular equilibrium geometries based on coupled-cluster calculations including quadruple excitations
2005
Using analytic gradient techniques and an additivity scheme for the various electron correlation contributions, i.e. core-correlation, contribution due to full treatment of triple excitations and contributions due to quadruple excitations calculated with different basis sets, the accuracy of computed geometrical parameters are analysed in comparison with experiment. For a test set of 12 closed-shell and 5 open-shell molecules, it is found that inclusion of quadruple excitations is essential to reach agreement with experiment. The mean error of 0.002 pm and the standard deviation of 0.040 pm of the present CCSD(T)/cc-pV6Z + core(CCSD(T)/cc-pCVQZ) + T/cc-pVTZ + Q/cc-pVDZ results for the close…
Anharmonic force fields from analytic CCSD(T) second derivatives: HOF and F2O
1999
The recent implementation of analytic second derivatives for CCSD(T) (coupled cluster theory with single and double excitations augmented by a perturbational treatment of connected triple excitations) has been combined with a numerical finite difference procedure to calculate cubic and semidiagonal quartic force fields. Computational details of this approach are outlined. Applications are reported for HOF and F2O. The CCSD(T) results are in excellent agreement with experiment and represent a substantial improvement over the results obtained from MP2 (Mo/ller–Plesset second-order perturbation theory).
Convergence of nuclear magnetic shieldings and one‐bond 1J(11 B 1H) indirect spin–spin coupling constants in small boron molecules
2018
Self‐consistent field Hartree–Fock (SCF‐HF), density functional theory (B3LYP, KT1, KT2, and KT3), and coupled‐cluster calculations of the nuclear magnetic shielding constants of BH and BH3 molecules have been conducted to characterize the convergence of individual results obtained with correlation‐ and polarization‐consistent basis sets. The individual 11B and 1H NMR parameters were estimated in the complete basis set limit and compared with benchmark literature results. The SCF‐HF and density functional theory B3LYP predicted boron shieldings and shielding anisotropies of BH significantly differed from the results obtained by coupled‐cluster with single, double, and perturbative treatment…
Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes.
2014
A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported b…
Karplus-Type Dependence of Vicinal119Sn-13C and119Sn-1H Spin-Spin Couplings in Organotin(IV) Derivatives: A DFT Study
2009
The empirical Karplus-type dependence of (3)J((119)Sn,(13)C) and (3)J((119)Sn,(1)H) couplings in organotin(IV) derivatives has been computationally validated by DFT methods both at the nonrelativistic and scalar ZORA relativistic level. A preliminary calibration of the computational protocols, by comparing experimental and calculated couplings for a Set Of Suitable rigid molecules, revealed their high predictive power: in particular, relativistic results for (3)J((119)Sn,(13)C) have a mean absolute error of just above 2 Hz, over a range of values up to about 70 Hz. The latter protocol has then been used to study in detail the influence of substituents and multiple paths connecting the coupl…