Transition moments between excited electronic states from the Hermitian formulation of the coupled cluster quadratic response function

Abstract

We introduce a new method for the computation of the transition moments between the excited electronic states based on the expectation value formalism of the coupled cluster theory [B. Jeziorski and R. Moszynski, Int. J. Quant. Chem. 48, 161 (1993)]. The working expressions of the new method solely employ the coupled cluster amplitudes. In the approximation adopted in the present paper the cluster expansion is limited to single, double, and linear triple excitations. The computed dipole transition probabilities for the singlet-singlet and triplet-triplet transitions in alkali earth atoms agree well with the available theoretical and experimental data. In contrast to the existing coupled cluster response theory, the matrix elements obtained by using our approach satisfy the Hermitian symmetry even if the excitations in the cluster operator are truncated. As a part of the numerical evidence for the new method, we report calculations of the transition moments between the excited triplet states which have not yet been reported in the literature within the coupled cluster theory. Slater-type basis sets constructed according to the correlation-consistency principle are used in our calculations.

arXiv comment23 pages, 5 figures

References in corpus (18)

• Abundances for metal-poor stars with accurate parallaxes I. Basic data
• Precise study of asymptotic physics with subradiant ultracold molecules
• Coherent Control of Bond Making
• Accurate calculations of Sr properties for a high-accuracy optical clock
• Interatomic potentials, electric properties, and spectroscopy of the ground and excited states of the Rb_2 molecule: Ab initio calculations and effect of a non-resonant field
• Photodissociation of ultracold diatomic strontium molecules with quantum state control
• Rovibrational dynamics of the strontium molecule in the A^1Σ_u^+, c^3Π_u, and a^3Σ_u^+ manifold from state-of-the-art ab initio calculations
• Generating Molecular Rovibrational Coherence by Two-Photon Femtosecond Photoassociation of Thermally Hot Atoms
• Experimental Mg I oscillator strengths and radiative lifetimes for astrophysical applications on metal-poor stars - New data for the Mg I b triplet
• Optimized production of ultracold ground-state molecules: Stabilization employing potentials with ion-pair character and strong spin-orbit coupling
• Femtosecond two-photon photoassociation of hot magnesium atoms: A quantum dynamical study using thermal random phase wavefunctions
• Nonadiabatic Effects in Ultracold Molecules via Anomalous Linear and Quadratic Zeeman Shifts
• Calculation of two-centre two-electron integrals over Slater-type orbitals revisited. I. Coulomb and hybrid integrals
• Calculation of two-centre two-electron integrals over Slater-type orbitals revisited. III. Case study of the beryllium dimer
• Control of Optical Transitions with Magnetic Fields in Weakly Bound Molecules
• Calculation of two-centre two-electron integrals over Slater-type orbitals revisited. II. Neumann expansion of the exchange integrals
• Transition properties from the Hermitian formulation of the coupled cluster polarization propagator
• Long-range interactions between an atom in its ground S state and an open-shell linear molecule

Cited by in corpus (6)

• Random Phase Approximation Applied to Many-Body Noncovalent Systems
• Calculation of Araki-Sucher correction for many-electron systems
• Combining Slater-type orbitals and effective core potentials
• Rank-reduced equation-of-motion coupled cluster triples: an accurate and affordable way of calculating electronic excitation energies
• Molecular properties from the explicitly connected expressions of the response functions within the coupled-cluster theory
• Spin-orbit coupling matrix elements from the explicitly connected expressions of the response functions within the coupled-cluster theory