Search results for "atomic physics"

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…

Pilot applications of internally contracted multireference coupled cluster theory, and how to choose the cluster operator properly.

2011

The internally contracted multireference coupled cluster (icMRCC) method allows a highly accurate description of both static and dynamic correlation with a computational scaling similar to single reference coupled cluster theory. The authors show that the method can lose its orbital invariance and size consistency when no special care is taken in the elimination of redundant excitations. Using the BeH(2) model system, four schemes are compared which differ in their treatment of linear dependencies between excitations of different rank (such as between singles and doubles). While the energy curves agree within tens of μE(h) when truncating the cluster operator at double excitations (icMRCCSD…

Electronic Excitation Energy Transfer in Multichromophoric Assemblies: A Single Molecule Insight

2009

In recent years, single molecule spectroscopy has provided novel insights into the fundamentals of electronic excitation energy transfer in molecular aggregates. In order of increasing structural complexity, we have studied simple molecular dimers and multichromophoric dendrimers. It will be shown that the combination of frequency-selective single molecule spectroscopy and confocal fluorescence microscopy at 1.4 K is a unique tool to study energy transfer processes in these systems. In particular, from the line widths of single molecule excitation spectra, rate constants of energy transfer can be deduced directly. A detailed analysis shows that, for several cases, the mechanism of energy tr…

Importance of Triples Contributions to NMR Spin–Spin Coupling Constants Computed at the CC3 and CCSDT Levels

2016

We present the first analytical implementation of CC3 second derivatives using the spin-unrestricted approach. This allows, for the first time, the calculation of nuclear spin–spin coupling constants (SSCC) relevant to NMR spectroscopy at the CC3 level of theory in a fully analytical manner. CC3 results for the SSCCs of a number of small molecules and their fluorine substituted derivatives are compared with the corresponding coupled cluster singles and doubles (CCSD) results obtained using specialized basis sets. For one-bond couplings the change when going from CCSD to CC3 is typically 1–3%, but much higher corrections were found for 1JCN in FCN, 15.7%, and 1JOF in OF2, 6.4%. The changes v…

H2 O, H2 , HF, F2 and F2 O nuclear magnetic shielding constants and indirect nuclear spin-spin coupling constants (SSCCs) in the BHandH/pcJ-n and BHa…

2009

Good performance of segmented contracted basis sets XZP, where X = D, T, Q and 5, for obtaining H(2)O, H(2), HF, F(2) and F(2)O nuclear isotropic shielding constants in the BHandH Kohn-Sham basis set limit was shown. The results of two- and three-parameter complete basis set limit extrapolation schemes were compared with experimental results, earlier literature data and benchmark ab initio results. Similar convergence patterns of shieldings obtained from calculations using general purpose XZP basis sets and from polarization-consistent basis sets pcS-n and pcJ-n, where n = 0, 1, 2, 3 and 4, designed to accurately predict magnetic properties were observed. On the contrary, the SSCCs were mor…

Theoretical nuclear spin-spin coupling constants using atom-atom polarizabilities.13CH and HH′ coupling constants of some [2.2.1] bicyclic compound…

1977

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…

Tracking the time-evolution of the electron distribution function in Copper by femtosecond broadband optical spectroscopy

2019

Multitemperature models are nowadays often used to quantify the ultrafast electron-phonon (boson) relaxations and coupling strengths in advanced quantum solids. To test their applicability and limitations, we perform systematic studies of carrier relaxation dynamics in copper, a prototype system for which the two-temperature model (TTM) was initially considered. Using broadband time-resolved optical spectroscopy, we study the time evolution of the electron distribution function, $f(E)$, over a large range of excitation densities. Following intraband optical excitation, $f(E)$ is found to be athermal over several 100 fs, with a substantial part of the absorbed energy already being transferre…

Orbital instabilities and spin-symmetry breaking in coupled-cluster calculations of indirect nuclear spin–spin coupling constants

2009

Abstract The effect of orbital instabilities is investigated for spin-symmetry breaking perturbations, namely the Fermi-contact (FC) and spin–dipole (SD) contributions to the indirect nuclear spin–spin coupling constants. For the CO and N 2 molecules the FC and SD contributions have been calculated and orbital-stability analyses for various interatomic distances have been carried out. This includes calculations at the Hartree–Fock self-consistent field (HF-SCF), coupled-cluster (CC) singles and doubles (CCSD), CC3, CCSD(T), CCSDT-4, CC singles, doubles, and triples (CCSDT) levels, and for the first time also at the CC singles, doubles, triples, and quadruples (CCSDTQ) level of theory. For c…

Spin-orbit coupling constants from coupled-cluster response theory

2000

A scheme for the calculation of spin-orbit coupling constants using coupled-cluster (CC) electronic structure methods is described based on response-theory expressions for transition properties. An implementation is reported for singlet–triplet transitions within the coupled-cluster singles and doubles (CCSD) approximation. An atomic mean-field representation of the spin-orbit interaction is used to simplify the calculation of spin-orbit coupling constants. Sample calculations are presented for spin-orbit couplings for the 11Σ+→13Π transitions for BH and AlH and for the 11A′→13A″ and the 13A″→11A″ transitions for the silylenes HSiX, X=F, Cl, Br, and are compared to results obtained from ful…