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Register a new userAb initio relativistic treatment of the intercombination $a^3Pi-X^1Sigma^+$ Cameron system of the CO molecule
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Added by
Alexander Oleynichenko
Publication date
2020
fields
Physics
and research's language is
English
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The intercombination $a^3Pi - X^1Sigma^+$ Cameron system of carbon monoxide has been computationally studied in the framework of multi-reference Fock space coupled cluster method with the use of generalized relativistic pseudopotential model for the effective introducing the relativity in all-electron correlation treatment. The extremely weak $a^3Pi_{Omega=0^+,1} - X^1Sigma^+$ transition probabilities and radiative lifetimes of the metastable $a^3Pi$ state were calculated and compared with their previous theoretical and experimental counterparts. The impact of a presumable variation of the fine structure constant $alpha=e^2/hbar c$ on transition strength of the Cameron system has been numerically evaluated as well.
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We observed the $A^1Sigma^+sim b^3Pito a^3Sigma^+/X^1Sigma^+$ laser-induced fluorescence (LIF) spectra of the RbCs molecule excited from the ground $X^1Sigma^+$ state by the Ti:Sapphire laser. The LIF radiation from the common perturbed levels of the singlet-triplet $Asim b$ complex was recorded by the Fourier-transform (FT) spectrometer with the instrumental resolution of 0.03~cm$^{-1}$. The relative intensity distribution in the rotationally resolved $Asim bto a^3Sigma^+(v_a)/X^1Sigma^+(v_X)$ progressions was measured, and their branching ratio was found to be about of 1$div$5$ times$10$^{-4}$ in the bound region of the $a^3Sigma^+$ and $X^1Sigma^+$ states. The experiment was complemented with the scalar and full relativistic calculations of the $A/b - X/a$ transition dipole moments (TDMs) as functions of internuclear distance. The relative systematic error in the resulting emph{ab initio} TDM functions evaluated for the strong $A - X$ transition was estimated as few percent in the energy region, where the experimental LIF intensities are relevant. The relative spectral sensitivity of the FT registration system, operated with the InGaAs diode detector and CaF beam-splitter, was calibrated in the range $[6~500,12~000]$~cm$^{-1}$ by a comparison of experimental intensities in the long $Asim bto X(v_X)$ LIF progressions of the K$_2$ and KCs molecules with their theoretical counterparts evaluated using the emph{ab initio} $A - X$ TDMs. Both experimental and theoretical transition probabilities can be employed to improve the stimulated Raman adiabatic passage process, $ato Asim b to X$, which is exploited for a laser assembling of ultracold RbCs molecules.
We present a combined experimental and theoretical study on the radiative lifetime of CO in the $a^3Pi_{1,2}, v=0$ state. CO molecules in a beam are prepared in selected rotational levels of this metastable state, Stark-decelerated and electrostatically trapped. From the phosphorescence decay in the trap, the radiative lifetime is measured to be $2.63pm0.03$ ms for the $a^3Pi_1, v=0, J=1$ level. From spin-orbit coupling between the $a^3Pi$ and the $A^1Pi$ state a 20% longer radiative lifetime of 3.16 ms is calculated for this level. It is concluded that coupling to other $^1Pi$ states contributes to the observed phosphorescence rate of metastable CO.
We present an implicit solvent model for ab initio electronic structure calculations which is fully self-consistent and is based on direct solution of the nonhomogeneous Poisson equation. The solute cavity is naturally defined in terms of an isosurface of the electronic density according to the formula of Fattebert and Gygi (J. Comp. Chem. 23, 6 (2002)). While this model depends on only two parameters, we demonstrate that by using appropriate boundary conditions and dispersion-repulsion contributions, solvation energies obtained for an extensive test set including neutral and charged molecules show dramatic improvement compared to existing models. Our approach is implemented in, but not restricted to, a linear-scaling density functional theory (DFT) framework, opening the path for self-consistent implicit solvent DFT calculations on systems of unprecedented size, which we demonstrate with calculations on a 2615-atom protein-ligand complex.
QMCPACK is an open source quantum Monte Carlo package for ab-initio electronic structure calculations. It supports calculations of metallic and insulating solids, molecules, atoms, and some model Hamiltonians. Implemented real space quantum Monte Carlo algorithms include variational, diffusion, and reptation Monte Carlo. QMCPACK uses Slater-Jastrow type trial wave functions in conjunction with a sophisticated optimizer capable of optimizing tens of thousands of parameters. The orbital space auxiliary field quantum Monte Carlo method is also implemented, enabling cross validation between different highly accurate methods. The code is specifically optimized for calculations with large numbers of electrons on the latest high performance computing architectures, including multicore central processing unit (CPU) and graphical processing unit (GPU) systems. We detail the programs capabilities, outline its structure, and give examples of its use in current research calculations. The package is available at http://www.qmcpack.org .
The accurate prediction of singlet and triplet excitation energies is of significant fundamental interest and is critical for many applications. An area of intense research, most calculations of singlet and triplet energies use time-dependent density functional theory (TDDFT) in conjunction with an approximate exchange-correlation functional. In this work, we examine and critically assess an alternative method for predicting low-lying neutral excitations with similar computational cost, the ab initio Bethe-Salpeter equation (BSE) approach, and compare results against high-accuracy wavefunction-based methods. We consider singlet and triplet excitations of 27 prototypical organic molecules, including members of Thiels set, the acene series, and several aromatic hydrocarbons exhibiting charge-transfer-like excitations. Analogous to its impact in TDDFT, we find that the Tamm-Dancoff approximation (TDA) overcomes triplet instabilities in the BSE approach, improving both triplet and singlet energetics relatively to higher level theories. Finally, we find that BSE-TDA calculations built on good DFT starting points, such as those utilizing optimally-tuned range-separated hybrid functionals, can yield accurate singlet and triplet excitation energies for gas-phase organic molecules.
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